Science.gov

Sample records for triplet state spectra

  1. Heisenberg spin exchange effects in powder spectra of weakly perturbed triplet states

    NASA Astrophysics Data System (ADS)

    Chesnut, D. B.; Meinholtz, Dore C.

    1985-12-01

    Heisenberg spin exchange effects on the powder spectra of weakly perturbed triplet states have been studied by simulation techniques. From very small exchange frequencies on, the derivative powder spectrum is dominated by a sharp, essentially constant width, central line whose amplitude exhibits very close to a square-root dependence on the exchange frequency. The derivative powder edge lines are shown to behave according to the single crystal limiting exchange width equation and it is shown that the frequency dependence of the central dominating line provides yet another measure of exchange parameters in physical systems. Application of these methods to the (φ3AsCH+3) (TCNQ)-2 ion radical salt yields results in good agreement with those obtained by other methods.

  2. 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.

  3. 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.

  4. Assignments of Lowest Triplet State in Ir Complexes by Observation of Phosphorescence Excitation Spectra at 6 K

    NASA Astrophysics Data System (ADS)

    Kodate, Satoshi; Suzuka, Isamu

    2006-01-01

    We tried the assignment of the origin of phosphorescent bands in Ir complexes. It is important to elucidate the luminescent mechanism in order to design organic light-emitting devices (OLEDs) besed on new materials. The Stokes shift between the phosphorescence and phosphorescence excitation spectra of Ir complexes such as fac-tris(2-phenylpyridine) iridium(III) [Ir(ppy)3], fac-tris(2-(2-thienyl)pyridine) iridium(III) [Ir(thpy)3], bis(2-phenylpyridine) iridium(III)benzo[h]quinoline [Ir(ppy)2bzq], fac-tris(benzo[h]quinoline) iridium(III) [Ir(bzq)3] and bis[(4,6-difluorophenyl)pyridinato](picolinato) iridium(III) [FIrpic] was measured in a solution and (phenyl)4Sn at 6 K. The amount of Stokes shift corresponds to the nature of the lowest triplet state. We discovered that the amount of Stokes shift clearly differs depending on whether the lowest triplet state of each Ir complex is triplet metal-to-ligand charge transfer (3MLCT) or 3π-π*. Namely, the case of 3MLCT shows a large shift, while the case of 3π-π* shows a small shift. We also present the resolved phosphorescence and phosphorescence excitation spectra of Ir complexes in (phenyl)4Sn. The sharp bands were assigned to the 3π-π* transition, and the broad bands were assigned to the 3MLCT state. The nature of the lowest triplet state is also discussed on the basis of resolved spectra.

  5. 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.

  6. 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.

  7. Properties of the Triplet State of Coumarin Substituted Compounds

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    PubMed

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

    2016-09-19

    Aromaticity reversal in the lowest triplet state, or Baird's rule, has been postulated for the past few decades. Despite numerous theoretical works on aromaticity reversal, experimental study is still at a rudimentary stage. Herein, we investigate the aromaticity reversal in the lowest excited triplet state using a comparable set of [26]- and [28]hexaphyrins by femtosecond time-resolved infrared (IR) spectroscopy. Compared to the relatively simple IR spectra of [26]bis(rhodium) hexaphyrin (R26H), those of [28]bis(rhodium) hexaphyrin (R28H) show complex IR spectra the region for the stretching modes of conjugated rings. Whereas time-resolved IR spectra of R26H in the excited triplet state are dominated by excited state IR absorption peaks, while those of R28H largely show ground state IR bleaching peaks, reflecting the aromaticity reversal in the lowest triplet state. These contrasting IR spectral features serve as new experimental aromaticity indices for Baird's rule. PMID:27510963

  9. Properties of chrysene in the higher triplet excited state

    NASA Astrophysics Data System (ADS)

    Cai, Xichen; Hara, Michihiro; Kawai, Kiyohiko; Tojo, Sachiko; Majima, Tetsuro

    2003-01-01

    Properties of chrysene in the higher triplet excited state were studied by the two-color two-laser flash photolysis method. Triplet energy transfers from chrysene in the higher triplet excited state to quenchers such as biphenyl and naphthalene, and from the quenchers in the triplet excited state back to chrysene in the ground state were observed to proceed at the diffusion-controlled rate. From dependence of the quenching efficiency on the quencher concentration, the lifetime of chrysene in the higher triplet excited state was estimated to be 60 ps with considering the time-dependent quenching.

  10. 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

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

  13. Triplet State Epr: AN Application to Three Iron - Flavoproteins.

    NASA Astrophysics Data System (ADS)

    Stevenson, Randy Claude

    This thesis is a comprehensive development of triplet spin Hamiltonians and the application of that formalism to the electron paramagnetic resonance (EPR) spectra of three iron-sulfur flavoproteins. These spectra developed only after the enzymes had been reduced with their substrates; the signals did not appear upon titration with other reducing agents such as dithionite. As a complement to that work, part of the thesis project included the further development of the multifrequency facilities at the University of Michigan. A new tunable 15 GHz EPR cavity for a P band spectrometer, a new 3 GHz cavity and a redesigned automatic frequency control unit (AFC) for an S band spectrometer contributed to the improvement and extension of the EPR capabilities. The data obtained from these spectrometers indicated that there was a spin-spin interaction due to two spin 1/2 systems, a singly reduced flavin and singly reduced {4Fe -4S} cluster, in a triplet state. Computer simulations confirmed that the interactions in trimethylamine dehydrogenase (TMAD), from a bacterium W3Al, and TMAD and dimethyamine dehydrogenase (DMAD) from a bacterium Hyphomicrobium X, are indeed spin-coupled triplet interactions. In addition, the computer simulations indicated that there was a distribution of zero field splittings among the various enzyme molecules constituting the samples, probably due to a variation in g anisotropy of the {4Fe-4S} center. However, these simulations represented only a phenomenological description. A plausible model for the spin-spin interaction, in terms of anisotropic exchange and magnetic dipole-dipole interactions, indicated that the structures of the paramagnetic sites among all three enzymes were very similar. The model limited the edge-edge interaction distance between reduced flavin and reduced {4Fe-4S} cluster to somewhere between 3 and 5 (ANGSTROM).

  14. 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

  15. On the influence of silver perchlorate on the lowest triplet state properties of N-vinylcarbazole

    NASA Astrophysics Data System (ADS)

    Zander, Maximilian

    1987-01-01

    N-vinylcarbazole is non-phosphorescent due to effective radiationless deactivation of the triplet state but forms a ground state complex with silver ions which is phosphorescent. Two different complexes are observed. From their phosphorescence spectra the T 1 state energy of N-vinylcarbazole is estimated to be 24000 cm -1.

  16. 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.

  17. 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.

  18. Ultracold triplet molecules in the rovibrational ground state.

    PubMed

    Lang, F; Winkler, K; Strauss, C; Grimm, R; Denschlag, J Hecker

    2008-09-26

    We report here on the production of an ultracold gas of tightly bound Rb2 triplet molecules in the rovibrational ground state, close to quantum degeneracy. This is achieved by optically transferring weakly bound Rb2 molecules to the absolute lowest level of the ground triplet potential with a transfer efficiency of about 90%. The transfer takes place in a 3D optical lattice which traps a sizeable fraction of the tightly bound molecules with a lifetime exceeding 200 ms. PMID:18851446

  19. 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

  20. 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

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

    PubMed

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

    2015-04-01

    The excited states of UV-B absorbers, ethylhexyl triazone (EHT) and diethylhexylbutamido triazone (DBT), have been studied through measurements of UV absorption, fluorescence, phosphorescence, triplet-triplet absorption and electron paramagnetic resonance spectra in ethanol. The energy levels of the lowest excited singlet (S1) and triplet (T1) states and quantum yields of fluorescence and phosphorescence of EHT and DBT were determined. In ethanol at 77 K, the deactivation process of EHT and DBT is predominantly fluorescence, however, a significant portion of the S1 molecules undergoes intersystem crossing to the T1 state. The observed phosphorescence spectra, T1 lifetimes and zero-field splitting parameters suggest that the T1 state of EHT can be assigned to a locally excited (3)ππ* state within p-(N-methylamino)benzoic acid, while the T1 state of DBT can be assigned to a locally excited (3)ππ* state within p-(N-methylamino)benzoic acid or p-amino-N-methylbenzamide. The quantum yields of singlet oxygen generation by EHT and DBT were determined by time-resolved near-IR phosphorescence measurements in ethanol at room temperature. EHT and DBT did not exhibit significantly antioxidative properties by quenching singlet oxygen, in contrast to the study by Lhiaubet-Vallet et al. PMID:25653197

  2. Photoexcited triplet states of new UV absorbers, cinnamic acid 2-methylphenyl esters.

    PubMed

    Kikuchi, Azusa; Saito, Haruo; Mori, Masao; Yagi, Mikio

    2011-12-01

    Phosphorescence spectra of nonphosphorescent or very weakly phosphorescent new UV absorbers, 2-methylphenyl cinnamate (MePC), 2-methylphenyl 4-methoxycinnamate (MePMC) and 2-methylphenyl 4-ethoxycinnamate (MePEC) have been observed by using external heavy atom effects of ethyl iodide in ethanol at 77 K. The lowest excited triplet (T(1)) energies of these new UV absorbers are lower than those of a widely used UV-A absorber, 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM), in both keto and enol forms. The intermolecular triplet-triplet energy transfer from photolabile BM-DBM to MePMC was observed by measuring the time-resolved phosphorescence spectra. Electron paramagnetic resonance spectra have been observed for the T(1) states of these new UV absorbers in ethanol at 77 K by using benzophenone as a triplet sensitizer. The observed T(1) lifetimes, zero-field splitting (ZFS) parameters and molecular orbital calculations of the ZFS parameters suggest that T(1) states of these new UV absorbers posses mainly (3)ππ* character. The deactivation processes of the lowest excited singlet (S(1)) states are predominantly fluorescence and internal conversion to the ground (G) states in MePMC and MePEC, while the main deactivation process of the S(1) state of MePC is internal conversion to the G state. The molar absorption coefficients of MePMC and MePEC in the UV-A and UV-B regions are larger than that of most widely used UV-B absorber, octyl methoxycinnamate. PMID:22002255

  3. 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

  4. 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

  5. p-Benzyne derivatives that have exceptionally small singlet-triplet gaps and even a triplet ground state.

    PubMed

    Clark, Aurora E; Davidson, Ernest R

    2003-05-01

    In an effort to find a p-benzyne (1,4-didehydrobenzene) derivative with a triplet ground state, we have investigated tetrasubstitution by -F, -NH(2), -CH(3), and -NO(2) groups. These were predicted to reduce the singlet-triplet gap, but none led to a triplet ground state because of unexpected destabilization of one of the radical orbitals. This effect is likely the result of rehybridization of the substituted C atom, which has been observed for substituted benzene and perturbs the side sigma and sigma* orbital energies of the phenyl ring. The role of substituent rotation on the energy difference between the two nominally singly occupied orbitals (S and A) was then investigated. The energy of the A radical orbital was found to be much more sensitive to perturbations within the sigma C[bond]C framework than the S MO. Consequently, we believe that rehybridization of the ring carbons destabilizes the A radical orbital and can lead to large singlet-triplet splittings. To test this hypothesis, calculations on a p-benzyne with 2,6 substitution by oxygen were performed. Interestingly, a triplet ground state was predicted. Yet, examination of the geometry and wave function showed that 2,6-quinone p-benzyne is a very twisted molecule with a C3-C4-C5 allene linkage and a C1 triplet carbene center.

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

    PubMed

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

    2012-08-01

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

  7. Room temperature triplet state spectroscopy of organic semiconductors.

    PubMed

    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

  8. 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

  9. Dark state experiments with ultracold, deeply-bound triplet molecules.

    PubMed

    Lang, Florian; Strauss, Christoph; Winkler, Klaus; Takekoshi, Tetsu; Grimm, Rudolf; Denschlag, Johannes Hecker

    2009-01-01

    We examine dark quantum superposition states of weakly bound Rb2 Feshbach molecules and tightly bound triplet Rb2 molecules in the rovibrational ground state, created by subjecting a pure sample of Feshbach molecules in an optical lattice to a bichromatic Raman laser field. We analyze, both experimentally and theoretically, the creation and dynamics of these dark states. Coherent wavepacket oscillations of deeply bound molecules in lattice sites, as previously observed by Lang et al. (Phys. Rev. Lett., 2008, 101, 133005), are suppressed due to laser-induced phase locking of molecular levels. This can be understood as the appearance of a novel multilevel dark state. In addition, the experimental methods developed help to determine important properties of our coupled atom/ laser system. PMID:20151548

  10. Triplet acetylenes as synthetic equivalents of 1,2-bicarbenes: phantom n,pi state controls reactivity in triplet photocycloaddition.

    PubMed

    Zeidan, Tarek A; Kovalenko, Serguei V; Manoharan, Mariappan; Clark, Ronald J; Ghiviriga, Ion; Alabugin, Igor V

    2005-03-30

    Diaryl acetylenes, in which one of the aryl groups is either a pyridine or a pyrazine, undergo efficient triplet state photocycloaddition to 1,4-cyclohexadiene with formation of 1,5-diaryl substituted tetracyclo[3.3.0.0(2,8).0(4,6)]octanes (homoquadricyclanes). In the case of pyrazinyl acetylenes, the primary homoquadricyclane products undergo a secondary photochemical rearangement leading to diaryl substituted tricyclo[3.2.1.0(4,6)]oct-2-enes. Mechanistic and photophysical studies suggest that photocycloaddition proceeds through an electrophilic triplet excited state whereas the subsequent rearrangement to the tricyclooctenes proceeds through a singlet excited state. Chemical and quantum yields for the cycloaddition, in general, correlate with the electron acceptor character of aryl substituents but are attenuated by photophysical factors, such as the competition between the conversion of acetylene singlet excited state into the reactive triplet excited states (intersystem crossing: ISC) and/or to the radical-anion (photoelectron transfer from the diene to the excited acetylene: PET). Dramatically enhanced ISC between pi-pi S(1) state and "phantom" n,pi triplet excited state is likely to be important in directing reactivity to the triplet pathway. The role of PET can be minimized by the judicious choice of reaction conditions (solvent, concentration, etc.). From a practical perspective, such reactions are interesting because "capping" of the triple bond with the polycyclic framework orients the terminal aryl (4-pyridyl, 4-tetrafluoropyridyl, phenyl, etc.) groups in an almost perfect 60 degrees angle and renders such molecules promising supramolecular building blocks, especially in the design of metal coordination polymers. PMID:15783209

  11. 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

  12. Intramolecular triplet energy transfer via higher triplet excited state during stepwise two-color two-laser irradiation.

    PubMed

    Oseki, Yosuke; Fujitsuka, Mamoru; Sakamoto, Masanori; Majima, Tetsuro

    2007-10-01

    We studied the energy transfer processes in the molecular array consisting of pyrene (Py), biphenyl (Ph2), and bisphthalimidethiophene (ImT), (Py-Ph2)2-ImT, during two-color two-laser flash photolysis (2-LFP). The first laser irradiation predominantly generates ImT in the lowest triplet excited state (ImT(T1)) because of the efficient singlet energy transfer from Py in the lowest singlet excited state to ImT and, then, intersystem crossing of ImT. ImT(T1) was excited to the higher triplet excited state (Tn) with the second laser irradiation. Then, the triplet energy was rapidly transferred to Py via a two-step triplet energy transfer (TET) process through Ph2. The efficient generation of Py(T1) was suggested from the nanosecond-picosecond 2-LFP. The back-TET from Py(T1) to ImT was observed for several tens of microseconds after the second laser irradiation. The estimated intramolecular TET rate from Py(T1) to ImT was as slow as 3.1 x 104 s-1. Hence, long-lived Py(T1) was selectively and efficiently produced during the 2-LFP.

  13. Conformational energetics of stable and metastable states formed by DNA triplet repeat oligonucleotides: Implications for triplet expansion diseases

    PubMed Central

    Völker, J.; Makube, N.; Plum, G. E.; Klump, H. H.; Breslauer, K. J.

    2002-01-01

    We have embedded the hexameric triplet repeats (CAG)6 and (CTG)6 between two (GC)3 domains to produce two 30-mer hairpins with the sequences d[(GC)3(CAG)6(GC)3] and d[(GC)3(CTG)6(GC)3]. This construct reduces the conformational space available to these repetitive DNA sequences. We find that the (CAG)6 and (CTG)6 repeats form stable, ordered, single-stranded structures. These structures are stabilized at 62°C by an average enthalpy per base of 1.38 kcal·mol−1 for the CAG triplet and 2.87 kcal·mol−1 for the CTG triplet, while being entropically destabilized by 3.50 cal·K−1·mol−1 for the CAG triplet and 7.6 cal·K−1·mol−1 for the CTG triplet. Remarkably, these values correspond, respectively, to 1/3 (for CAG) and 2/3 (for CTG) of the enthalpy and entropy per base values associated with Watson–Crick base pairs. We show that the presence of the loop structure kinetically inhibits duplex formation from the two complementary 30-mer hairpins, even though the duplex is the thermodynamically more stable state. Duplex formation, however, does occur at elevated temperatures. We propose that this thermally induced formation of a more stable duplex results from thermal disruption of the single-stranded order, thereby allowing the complementary domains to associate (perhaps via “kissing hairpins”). Our melting profiles show that, once duplex formation has occurred, the hairpin intermediate state cannot be reformed, consistent with our interpretation of kinetically trapped hairpin structures. The duplex formed by the two complementary oligonucleotides does not have any unusual optical or thermodynamic properties. By contrast, the very stable structures formed by the individual single-stranded triplet repeat sequences are thermally and thermodynamically unusual. We discuss this stable, triplet repeat, single-stranded structure and its interconversion with duplex in terms of triplet expansion diseases. PMID:12417759

  14. 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.

  15. 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

  16. Molecular adaptation of photoprotection: triplet states in light-harvesting proteins.

    PubMed

    Gall, Andrew; Berera, Rudi; Alexandre, Maxime T A; Pascal, Andrew A; Bordes, Luc; Mendes-Pinto, Maria M; Andrianambinintsoa, Sandra; Stoitchkova, Katerina V; Marin, Alessandro; Valkunas, Leonas; Horton, Peter; Kennis, John T M; van Grondelle, Rienk; Ruban, Alexander; Robert, Bruno

    2011-08-17

    The photosynthetic light-harvesting systems of purple bacteria and plants both utilize specific carotenoids as quenchers of the harmful (bacterio)chlorophyll triplet states via triplet-triplet energy transfer. Here, we explore how the binding of carotenoids to the different types of light-harvesting proteins found in plants and purple bacteria provides adaptation in this vital photoprotective function. We show that the creation of the carotenoid triplet states in the light-harvesting complexes may occur without detectable conformational changes, in contrast to that found for carotenoids in solution. However, in plant light-harvesting complexes, the triplet wavefunction is shared between the carotenoids and their adjacent chlorophylls. This is not observed for the antenna proteins of purple bacteria, where the triplet is virtually fully located on the carotenoid molecule. These results explain the faster triplet-triplet transfer times in plant light-harvesting complexes. We show that this molecular mechanism, which spreads the location of the triplet wavefunction through the pigments of plant light-harvesting complexes, results in the absence of any detectable chlorophyll triplet in these complexes upon excitation, and we propose that it emerged as a photoprotective adaptation during the evolution of oxygenic photosynthesis.

  17. Resonance Raman characterization of the radical anion and triplet states of zinc tetraphenylporphine

    SciTech Connect

    Reed, R.A.; Purrello, R.; Prendergast, K.; Spiro, T.G. )

    1991-11-28

    The photophysical properties of metalloporphyrins are important to a range of current research areas, ranging from solar energy conversion to photodynamic therapy. Resonance Raman (RR) spectra are reported for the anion radical and for the photoexcited triplet state of ZnTPP. RR spectra were obtained by excitation at 457.9 nm, at the anion absorption band maximum. Bands were assigned with the aid of pyrrole-d[sub 8] and phenyl-d[sub 20] isotopomers. The pattern of isotope shifts and polarizations was found to be quite similar to that of the neutral parent, ZnTPP. The frequency shift pattern is discussed in terms of the expectations for placing an electron in the e[sub g]* orbital, including the anticipated Jahn-Teller (J-T) effect. Although band overlaps make depolarization ratios difficult to quantitate, the [nu][sub 10] band is found to be essentially depolarized, indicating that the J-T effect is dynamic, rather than static in character, at least with respect to stretching of the C[sub a]C[sub m] bonds. The [nu][sub 2] and [nu][sub 10] downshifts are attributable to porphyrin core expansion upon reduction, but the [nu][sub 27] and [nu][sub 29] reductions are probably manifestations of the J-T effect. Triplet-state RR spectra were produced with 416-nm photolysis and 459-nm probe pulses (7 ns). The RR peaks were assigned via their polarizations and the d[sub 8] and d[sub 20] isotopomer shifts. The spectrum contains three strong bands of predominantly phenyl character. Their frequencies are unshifted relative to the ground state, implying negligible electronic involvement of the phenyl groups in the T[sub 1] state, but their enhancements indicate substantial involvement in the resonant T[sub n] state. This state is suggested to be produced by charge transfer from the porphyrin e[sub g]* to the phenyl [pi]* orbitals.

  18. 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.

  19. 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

  20. Switching of the triplet excited state of rhodamine/naphthaleneimide dyads: an experimental and theoretical study.

    PubMed

    Cui, Xiaoneng; Zhao, Jianzhang; Lou, Zhangrong; Li, Shujing; Wu, Huijian; Han, Ke-Li

    2015-01-01

    Rhodamine-bromonaphthaleneimide (RB-NI) and rhodamine-bromonaphthalenediimide (RB-NDI) dyads were prepared for switching of the triplet excited states. Bromo-NI or bromo-NDI parts in the dyads are the spin converters, i.e., the triplet state producing modules, whereas the RB unit is the acid-activatable electron donor/energy acceptor. NI and NDI absorb at 359 and 541 nm, and the T1 state energy levels are 2.25 and 1.64 eV, respectively. RB undertakes the reversible spirolactam (RB-c) ↔ opened amide (RB-o) transformation. RB-c shows no visible light absorption, and the triplet-state energy level is ET1 = 3.36 eV. Conversely RB-o shows strong absorption at 557 nm, and ET1 is 1.73 eV. Thus, the acid-activated fluorescence-resonance-energy-transfer (FRET) competes with the ISC of NI or NDI. No triplet state was observed for the dyads with nanosecond time-resolved transient absorption spectroscopy. Upon addition of acid, strong fluorescence and long-living triplet excited states were observed. Thus, the producing of triplet state is acid-activatable. The triplet state of RB-NI is localized on RB-o part, whereas in RB-NDI the triplet state is delocalized on both the NDI and RB-o units. The ISC of spin converter was not outcompeted by RET. These studies are useful for switching of triplet excited state. PMID:25436874

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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)

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  11. 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.

  12. Dye-triplet-state and singlet-oxygen quenching effects in solid state dye lasers

    NASA Astrophysics Data System (ADS)

    King, Terence A.; Ahmad, Mohammad; Gorman, Anthony; Hamblett, I.; Rahn, Mark D.

    2000-04-01

    The main photodegradation mechanisms of pyrromethene 567 are discussed, and the quantum efficiency of self-sensitized photo-oxidation, the predominant mechanism, was found to be 0.5% in aerated benzene-d6. Other degradation mechanisms do exist, but the high photostability of the dye in solid host media possibly implies that they are all diffusion controlled. Solid-state dye lasers based on pyrromethene 567 doped poly(methyl methacrylate) with an added singlet oxygen quencher 1,4-diazobicyclo [2,2,2] octane showed a lifetime of 550,000 pulses. A triplet quencher, perylene, provided no improvement. Singlet oxygen quenching is effective in the solid-state whereas triplet quenching is not, presumably due to the slower diffusion rate of dye molecules compared with oxygen.

  13. 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

  14. 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.

  15. 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

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

    PubMed

    Kondakov, Denis Y

    2015-06-28

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

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

    NASA Astrophysics Data System (ADS)

    da Costa, G. S.

    2016-07-01

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

  18. Multi-triplet bound states and finite-temperature dynamics in highly frustrated quantum spin ladders

    NASA Astrophysics Data System (ADS)

    Honecker, Andreas; Mila, Frédéric; Normand, B.

    2016-09-01

    Low-dimensional quantum magnets at finite temperatures present a complex interplay of quantum and thermal fluctuation effects in a restricted phase space. While some information about dynamical response functions is available from theoretical studies of the one-triplet dispersion in unfrustrated chains and ladders, little is known about the finite-temperature dynamics of frustrated systems. Experimentally, inelastic neutron scattering studies of the highly frustrated two-dimensional material SrCu2(BO3)2 show an almost complete destruction of the one-triplet excitation band at a temperature only 1/3 of its gap energy, accompanied by strong scattering intensities for apparent multi-triplet excitations. We investigate these questions in the frustrated spin ladder and present numerical results from exact diagonalization for the dynamical structure factor as a function of temperature. We find anomalously rapid transfer of spectral weight out of the one-triplet band and into both broad and sharp spectral features at a wide range of energies, including below the zero-temperature gap of this excitation. These features are multi-triplet bound states, which develop particularly strongly near the quantum phase transition, fall to particularly low energies there, and persist all the way to infinite temperature. Our results offer valuable insight into the physics of finite-temperature spectral functions in SrCu2(BO3)2 and many other highly frustrated spin systems.

  19. Nonradiative deactivation of the lowest excited triplet state of the dibenzo- p-dioxin molecule

    NASA Astrophysics Data System (ADS)

    Gastilovich, E. A.; Klimenko, V. G.; Volkova, L. V.; Nurmukhametov, R. N.

    2011-11-01

    In the nonadiabatic approximation, we study how intramolecular interactions affect the nonradiative energy degradation T {1/ s } ↝ S 0 of triplet sublevels s of the lowest triplet state of the dibenzo- p-dioxin molecule. We consider the role played in the degradation by the shape of promoting high- and low-frequency vibrational modes and by spin-orbit interactions separately in the carbon backbone of the molecule and in heteroatoms (oxygen). We find that σ-electrons of oxygen that correspond to the lone pair and to valence electrons play different roles in the nonadiabatic interaction.

  20. 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

  1. 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.

  2. Measurements and Analysis of Helium-Like Triplet Ratios in the X-Ray Spectra of O-Type Stars

    SciTech Connect

    Leutenegger, Maurice A.; Paerels, Frits B.S.; Kahn, Steven M.; Cohen, David H.; /Swarthmore Coll.

    2006-06-19

    We discuss new methods of measuring and interpreting the forbidden-to-intercombination line ratios of helium-like triplets in the X-ray spectra of O-type stars, including accounting for the spatial distribution of the X-ray emitting plasma and using the detailed photospheric UV spectrum. Measurements are made for four O stars using archival Chandra HETGS data. We assume an X-ray emitting plasma spatially distributed in the wind above some minimum radius R{sub 0}. We find minimum radii of formation typically in the range of 1.25 < R{sub 0}/R{sub *} < 1.67, which is consistent with results obtained independently from line profile fits. We find no evidence for anomalously low f/i ratios and we do not require the existence of X-ray emitting plasmas at radii that are too small to generate sufficiently strong shocks.

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

    SciTech Connect

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

    1997-08-01

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

  4. 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.

  5. 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.

  6. 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.

  7. Quenching of ππ* triplet states of vaporous polycyclic aromatic compounds by oxygen

    NASA Astrophysics Data System (ADS)

    Zalesskaya, G. A.; Kuchinskiĭ, A. V.

    2007-05-01

    The oxygen quenching rate constants k T O2 of the triplet state T 1 of vapors of polycyclic aromatic hydrocarbons (PAHs) with strongly different oxidation potentials 0.44 eV < E OX < 1.61 eV and energies of the triplet levels 14800 cm-1 < E T < 24500 cm-1 (anthracene, 2-aminoanthracene, 9-nitroanthracene, chrysene, phenanthrene, fluoranthene, and carbazole) are estimated from the measured dependences of the decay rates and intensities of delayed fluorescence on the oxygen pressure P O2. It is found that the rate constants k T O2 vary from 4 × 103 (9-nitroanthracene) to 4 × 105 s-1 Torr-1 (2-aminoanthracene) and increase with decreasing oxidation potentials E OX of PAHs. The rate constants k T O2 for vapors and solutions are compared. The dependences of k T O2 on the free energy of two intermolecular processes, namely, triplet energy transfer to oxygen and electron transfer, are analyzed. It is shown that the rate constants k T O2 increase with decreasing electron transfer free energy, which proves that, along with energy transfer, charge-transfer interactions contribute to the quenching of the triplet states of PAH vapors.

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

    PubMed Central

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

    2016-01-01

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

  9. High-resolution spectroscopy and quantum-defect model for the gerade triplet np and nf Rydberg states of He{sub 2}

    SciTech Connect

    Sprecher, D.; Liu, J.; Krähenmann, T.; Schäfer, M.; Merkt, F.

    2014-02-14

    Photoionization spectra and Rydberg-state-resolved threshold-ionization spectra of the gerade triplet np Rydberg states of {sup 4}He{sub 2} located in the vicinity of the X{sup +2}Σ{sub u}{sup +}(ν{sup +} =0) ionization threshold were recorded from the 2sσa{sup 3}Σ{sub u}{sup +} metastable state. An accuracy of 0.01 cm{sup −1} was achieved for the experimental term values of the observed Rydberg states. The data were combined with spectroscopic data on low-lying triplet np and nf Rydberg states from the literature to derive energy- and internuclear-distance-dependent eigenquantum-defect parameters of multichannel quantum-defect theory (MQDT). The MQDT calculations reproduce the experimental data within their experimental uncertainties and enabled the derivation of potential-energy curves for the lowest triplet p Rydberg states (n = 2–5) of He{sub 2}. The eigenquantum-defect parameters describing the p -f interaction were found to be larger than 0.002 at the energies corresponding to the high-n Rydberg states, so that the p -f interaction plays an important role in the autoionization dynamics of np Rydberg states with ν{sup +} = 0. By extrapolating the experimental term values of triplet np Rydberg states of {sup 4}He{sub 2} in the range of principal quantum number n between 87 and 110, the positions of the (ν{sup +} = 0, N{sup +} = 3) and (ν{sup +} = 0, N{sup +} = 5) levels of the ground state of {sup 4}He{sub 2}{sup +} were determined to lie 70.937(3) cm{sup −1} and 198.369(6) cm{sup −1}, respectively, above the (ν{sup +} = 0, N{sup +} = 1) ground rotational level.

  10. 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.

  11. 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.

  12. Delayed fluorescence during the deactivation of highly excited triplet states

    SciTech Connect

    Skvortsov, V.I.; Alfimov, M.V.

    1987-06-01

    It has been suggested that the T state may be not only an electron donor but an acceptor, i.e., it may give a charge transfer state in a photoreduction reaction: A(T) + M ..-->.. /sup 3/(A/sup .-/M/sup +./). In this connection, it may be assumed that the quenching may also be connected with the nonradiative deactivation of excitation energy in charge transfer states (A/sup .-/M/sup +./). Aromatic molecules are characterized by an extremely low quantum yield for intramolecular intersystem crossing. However, in charge-transfer states the efficiency of intersystem crossing may be enhanced. The authors have investigated the laws governing DF in conditions where the deactivation of T states occurs. The systems studied were frozen (77 K) solutions of the aromatic additives naphthalene, diphenyl, and chrysene in toluene, MCH, and ethanol.

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

    SciTech Connect

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

    1995-08-02

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

  14. 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

  15. Probing the C₆₀ triplet state coupling to nuclear spins inside and out.

    PubMed

    Filidou, Vasileia; Mamone, Salvatore; Simmons, Stephanie; Karlen, Steven D; Anderson, Harry L; Kay, Christopher W M; Bagno, Alessandro; Rastrelli, Federico; Murata, Yasujiro; Komatsu, Koichi; Lei, Xuegong; Li, Yongjun; Turro, Nicholas J; Levitt, Malcolm H; Morton, John J L

    2013-09-13

    The photoexcitation of functionalized fullerenes to their paramagnetic triplet electronic state can be studied by pulsed electron paramagnetic resonance (EPR) spectroscopy, whereas the interactions of this state with the surrounding nuclear spins can be observed by a related technique: electron nuclear double resonance (ENDOR). In this study, we present EPR and ENDOR studies on a functionalized exohedral fullerene system, dimethyl[9-hydro (C60-Ih)[5,6]fulleren-1(9H)-yl]phosphonate (DMHFP), where the triplet electron spin has been used to hyperpolarize, couple and measure two nuclear spins. We go on to discuss the extension of these methods to study a new class of endohedral fullerenes filled with small molecules, such as H₂@C₆₀, and we relate the results to density functional calculations. PMID:23918718

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

    NASA Astrophysics Data System (ADS)

    Terazima, Masahide; Yamauchi, Seigo; Hirota, Noboru

    1985-10-01

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

  17. 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.

  18. Inelastic and elastic collision rates for triplet states of ultracold strontium

    NASA Astrophysics Data System (ADS)

    Traverso, A.; Chakraborty, R.; Martinez de Escobar, Y. N.; Mickelson, P. G.; Nagel, S. B.; Yan, M.; Killian, T. C.

    2009-06-01

    We report measurement of the inelastic and elastic collision rates for S88r atoms in the (5s5p)P30 state in a crossed-beam optical dipole trap. Since the (5s5p)P30 state is the lowest level of the triplet manifold, large loss rates indicate the importance of principle-quantum-number-changing collisions at short range. We also provide an estimate of the collisional loss rates for the (5s5p)P32 state. Large loss-rate coefficients for both states indicate that evaporative cooling toward quantum degeneracy in these systems is unlikely to be successful.

  19. 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

  20. Long-lived room-temperature deep-red-emissive intraligand triplet excited state of naphthalimide in cyclometalated Ir(III) complexes and its application in triplet-triplet annihilation-based upconversion.

    PubMed

    Sun, Jifu; Wu, Wanhua; Zhao, Jianzhang

    2012-06-25

    Cyclometalated Ir(III) complexes with acetylide ppy and bpy ligands were prepared (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine) in which naphthal (Ir-2) and naphthalimide (NI) were attached onto the ppy (Ir-3) and bpy ligands (Ir-4) through acetylide bonds. [Ir(ppy)(3)] (Ir-1) was also prepared as a model complex. Room-temperature phosphorescence was observed for the complexes; both neutral and cationic complexes Ir-3 and Ir-4 showed strong absorption in the visible range (ε=39,600  M(-1)  cm(-1) at 402 nm and ε=25,100  M(-1)  cm(-1) at 404 nm, respectively), long-lived triplet excited states (τ(T)=9.30 μs and 16.45 μs) and room-temperature red emission (λ(em)=640 nm, Φ(p)=1.4 % and λ(em)=627 nm, Φ(p)=0.3 %; cf. Ir-1: ε=16,600  M(-1)  cm(-1) at 382 nm, τ(em)=1.16 μs, Φ(p)=72.6 %). Ir-3 was strongly phosphorescent in non-polar solvent (i.e., toluene), but the emission was completely quenched in polar solvents (MeCN). Ir-4 gave an opposite response to the solvent polarity, that is, stronger phosphorescence in polar solvents than in non-polar solvents. Emission of Ir-1 and Ir-2 was not solvent-polarity-dependent. The T(1) excited states of Ir-2, Ir-3, and Ir-4 were identified as mainly intraligand triplet excited states ((3)IL) by their small thermally induced Stokes shifts (ΔE(s)), nanosecond time-resolved transient difference absorption spectroscopy, and spin-density analysis. The complexes were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion and quantum yields of 7.1 % and 14.4 % were observed for Ir-2 and Ir-3, respectively, whereas the upconversion was negligible for Ir-1 and Ir-4. These results will be useful for designing visible-light-harvesting transition-metal complexes and for their applications as triplet photosensitizers for photocatalysis, photovoltaics, TTA upconversion, etc.

  1. Triplet Pair Correlations in s-Wave Superfluids as a Signature of the Fulde-Ferrell-Larkin-Ovchinnikov State

    NASA Astrophysics Data System (ADS)

    Zapata, I.; Sols, F.; Demler, E.

    2012-10-01

    We show that antiparallel triplet pairing correlations are generated in superfluids with purely s-wave interactions whenever population imbalance enforces anisotropic Fulde-Ferrell (FF) or inhomogeneous Larkin-Ovchinikov (LO) states. These triplet correlations appear in the Cooper pair wave function, while the triplet part of the gap remains zero. The same set of quasiparticle states contributes to the triplet component and to the polarization, thus spatially correlating them. In the LO case, this set forms a narrow band of Andreev states centered on the nodes of the s-wave order parameter. This picture naturally provides a unifying explanation of previous findings that attractive p-wave interaction stabilizes FFLO states. We also study a similar triplet mixing which occurs when a balanced two-component system displays FFLO-type oscillations due to a spin-dependent optical lattice. We discuss how this triplet component can be measured in systems of ultracold atoms using a rapid ramp across a p-wave Feshbach resonance. This should provide a smoking gun signature of FFLO states.

  2. 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.

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

    SciTech Connect

    Peterson, Kirk A.; Francisco, Joseph S.

    2014-01-28

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

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

    PubMed

    Michałek, G; Bułka, B R

    2011-05-01

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

  5. 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

  6. 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

  7. One-dimensional extended Hubbard model with spin-triplet pairing ground states

    NASA Astrophysics Data System (ADS)

    Tanaka, Akinori

    2016-10-01

    We show that the one-dimensional extended Hubbard model has saturated ferromagnetic ground states with the spin-triplet electron pair condensation in a certain range of parameters. The ground state wave functions with fixed electron numbers are explicitly obtained. We also construct two ground states in which both the spin-rotation and the gauge symmetries are broken, and show that these states are transferred from one to the other by applying the edge operators. The edge operators are reduced to the Majorana fermions in a special case. These symmetry breaking ground states are shown to be stabilized by a superconducting mean field Hamiltonian which is related to the Kitaev chain with the charge-charge interaction.

  8. 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.

  9. 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.

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

    PubMed

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

    2016-09-21

    Introducing bridging ligands such as DABCO to solutions of linear zinc porphyrin oligomers has previously been shown to lead to the formation of ladder-type assemblies in which the single porphyrin units in each strand adopt a predominantly co-planar conformation. Here, we employ transient Electron Paramagnetic Resonance (EPR) to study photogenerated triplet states of these complexes in frozen solution with a particular focus on the extent of spin delocalisation. We make use of two different techniques: (i) the zero-field splitting parameters D and E are determined using transient continuous wave (cw) EPR spectroscopy and (ii) the hyperfine coupling constants, which directly reveal the extent of spin delocalisation, are quantified by orientation-selective proton Electron Nuclear DOuble Resonance (ENDOR) spectroscopy. It is found that ladder formation does not encourage triplet state delocalisation either across the bridging ligand DABCO or along the individual porphyrin strands despite their co-planar conformation, which was previously shown to allow increased electronic delocalisation. PMID:27533592

  11. 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.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  14. 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.

  15. 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

  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) .

  17. Time-resolved EPR and optical studies of intermoiety interactions in the lowest triplet state of L-shaped dimers of naphthalene: Conformation dependence of excitation exchange interaction

    SciTech Connect

    Terazima, Masahide; Cai, Jianjian; Lim, E.C.

    2000-03-02

    Time-resolved EPR (TREPR), transient absorption, and phosphorescence spectra have been measured in solid matrixes at 77 K for the covalently linked L-shaped dimers of naphthalene, in which the in-plane long axes of the two naphthalene moieties are parallel and the in-plane short axes make an angle. The zero-field splitting (ZFS) parameters obtained by simulation of the TREPR spectra are consistent with the dimer geometries, if it is assumed that excitation exchange interaction is responsible for the small D values of the dimers relative to the monomer. The tilt angle in the triplet state is significantly smaller for the dimers exhibiting excimeric phosphorescence than those exhibiting monomeric emissions. Comparison of the spectral position and lifetime of phosphorescence from the L-shaped dimers with those from the sandwich dimers indicates that the excitation exchange interaction is substantially greater for the L-shaped dimers as compared to the sandwich dimers. The proposal that the preferred conformation of the triplet excimer of naphthalene is L-shaped, rather than sandwich, is supported by the measurements.

  18. The Nature of the Singlet and Triplet States of Cyclobutadiene as Revealed by Quantum Interference.

    PubMed

    Fantuzzi, Felipe; Cardozo, Thiago M; Nascimento, Marco A C

    2016-01-18

    The generalized product function energy partitioning (GPF-EP) method is applied to the description of the cyclobutadiene molecule. The GPF wave function was built to reproduce generalized valence bond (GVB) and spin-coupled (SC) wave functions. The influence of quasiclassical and quantum interference contributions to each chemical bond of the system are analyzed along the automerization reaction coordinate for the lowest singlet and triplet states. The results show that the interference effect on the π space reduces the electronic energy of the singlet cyclobutadiene relative to the second-order Jahn-Teller distortion, which takes the molecule from a D4h to a D2h structure. Our results also suggest that the π space of the (1) B1g state of the square cyclobutadiene is composed of a weak four center-four electron bond, whereas the (3) A2g state has a four center-two electron π bond. Finally, we also show that, although strain effects are nonnegligible, the thermodynamics of the main decomposition pathway of cyclobutadiene in the gas phase is dominated by the π space interference.

  19. Reaction of the m-THPC triplet state with the antioxidant Trolox and the anesthetic Propofol: modulation of photosensitization mechanisms relevant to photodynamic therapy?

    PubMed

    Friaa, O; Maillard, P; Brault, D

    2012-04-01

    Antioxidants may affect the outcome of photodynamic therapy (PDT) through the inactivation of reactive oxygen species. Their direct interaction with photosensitizers excited at the triplet state is also worthy of interest. This process is investigated by laser flash photolysis of m-THPC (meso-tetra(3-hydroxyphenyl)chlorin, Foscan) hydroalcoholic solutions added with Trolox (TrOH), a standard antioxidant or Propofol (PfOH, Diprivan(®)), a common anesthetic agent also characterized for its antioxidant properties. Transient UV-visible absorption spectra, kinetics at selected wavelengths and final spectra after extensive laser irradiation show that both compounds react with the m-THPC triplet state, (3)m-THPC, to ultimately restore the photosensitizer in its ground state. For PfOH, this process mainly appears as a single step obeying pseudo-first order kinetics. The bimolecular rate constant for the quenching of (3)m-THPC by PfOH is around 2 × 10(6) M(-1) s(-1), a value increased to some extent by the water content of the solution. A bimolecular reaction between (3)m-THPC and TrOH is observed with a rate constant of similar magnitude and dependence upon water. However, the reaction leads, at least partly, to intermediate species assigned to the TrO˙ radical and the m-THPC anion radical. Within a few ms, these species back react to yield m-THPC in its ground state. A general mechanism involving an intermediate activated complex with some charge transfer character is proposed. Depending on the redox potentials for the oxidation of the antioxidant, this complex evolves predominantly either toward the formation of radicals (TrOH) or back to the photosensitizer ground state (PfOH). Notably, the kinetics data suggest that Propofol may quench (3)m-THPC at concentrations relevant of clinical situation in PDT involving anesthesia. PMID:22307091

  20. Involvement of triplet state in the photodissociation of hydrogen peroxide: experimental evidence from time-resolved EPR study

    NASA Astrophysics Data System (ADS)

    Bhattacharjee, B.; Das, Ranjan

    The dissociation of photoexcited hydrogen peroxide to generate a pair of hydroxyl radicals is generally believed to take place in a repulsive electronic singlet state. The results presented here, based on time-resolved EPR experiments on the spin polarisation pattern of the acetone ketyl radical (CH3)2C•OH, generated on photodissociation of H2O2 in 2-propanol with a 248 nm laser light, strongly indicate significant involvement of a repulsive triplet state of excited hydrogen peroxide.

  1. 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.

  2. Intensity dependence of the excited state lifetimes and triplet conversion yield in the Fenna-Matthews-Olson antenna protein.

    PubMed

    Orf, Gregory S; Niedzwiedzki, Dariusz M; Blankenship, Robert E

    2014-02-27

    The Fenna-Matthews-Olson (FMO) protein is a soluble light-harvesting, bacteriochlorophyll a (BChl a) containing antenna complex found in green sulfur bacteria. We have measured time-resolved fluorescence and transient absorption at variable laser intensities at 298 and 77 K using FMO protein from Chlorobaculum tepidum prepared in both oxidizing and reducing environments. Fitting of the spectroscopic data shows that high laser intensities (i.e., above 10(13) photons × cm(-2) delivered per laser pulse) distort the intrinsic decay processes in this complex. At high laser intensities, both oxidized and reduced FMO samples behave similarly, exhibiting high levels of singlet-singlet annihilation. At lower laser intensities, the reduced protein mainly displays a singlet excited state lifetime of 2 ns, although upon oxidation, a 60 ps lifetime dominates. We also demonstrate that the apparent quantum yield of singlet-triplet intersystem crossing in the reduced FMO complex is ∼11% in the most favorable low laser intensities, with this yield decreasing and the probability of singlet-singlet annihilation yield increasing as laser intensity increases. After correcting for stimulated emission effects in the experiments, the actual maximum triplet yield is calculated to be ∼27%. Experiments at 77 K demonstrate that BChl a triplet states in FMO are localized on pigments no. 4 or 3, the lowest energy pigments in the complex. This study allows for a discussion of how BChl triplets form and evolve on the picosecond-to-nanosecond time scale, as well as whether triplet conversion is a physiologically relevant process.

  3. Photoreduction and light-induced triplet-state formation in a single-site fluoroalkylated zinc phthalocyanine.

    PubMed

    Moons, Hans; Loas, Andrei; Gorun, Sergiu M; Van Doorslaer, Sabine

    2014-10-28

    Electron-withdrawing perfluoroalkyl peripheral substituents enhance the photosensitizing properties of metal phthalocyanines while increasing their solubility, thus providing opportunities for advanced characterization of their catalytically-relevant excited states. Optical absorption and electron paramagnetic resonance (EPR) spectroscopy experiments reveal that red light induces the reduction of perfluoroisopropyl-substituted zinc(ii) phthalocyanine (F64PcZn) dissolved in ethanol. A similar photoreduction does not occur in toluene. Furthermore, intense UV irradiation causes the photodegradation of F64PcZn in ethanol, but low power UV illumination favours the formation of the triplet excited state, a prerequisite for new photocatalytic applications. The UV-induced triplet state of F64PcZn is characterized using a combination of transient EPR experiments and DFT computations. PMID:24842295

  4. Photoexcited triplet state provides a quantitative measure of intercalating drug-DNA binding energies

    NASA Astrophysics Data System (ADS)

    Maki, August H.; Alfredson, T. V.; Waring, M. J.

    1992-04-01

    A linear correlation between spectroscopic and thermodynamic properties of systems is rarely encountered. In triplet state ODMR studies of various DNA complexes of echinomycin, a quinoxaline-containing cyclic depsipeptide bis-intercalating antibiotic, and its biosynthesized quinoline analogs, such correlations are observed. The zero field splitting D-parameter of the intercalated quinoxaline or quinoline residue varies linearly with the free energy of drug-DNA complexing. From previous work, the DNA sequence specificity of echinomycin analogs is known to be influenced by the identity of the intercalating residue (e.g., quinoxaline vs. quinoline). The present results strongly suggest that the DNA sequence-specificity of these drugs is controlled largely by the intercalated residue, and that the energetics of the peptide- DNA interaction, although considerable, are relatively sequence independent. These conclusions run counter to the generally accepted idea that DNA recognition by sequence- seeking proteins is controlled by specific hydrogen bonding interactions. The high degree of N-methylation of the echinomycin peptide portion severely restricts these interactions, however. A simple theoretical model is presented to support the experimentally observed linear correlation between (Delta) D and (Delta) G.

  5. Transient IR Spectroscopic Observation of Singlet and Triplet States of 2-Nitrofluorene: Revisiting the Photophysics of Nitroaromatics.

    PubMed

    Larsen, Martin A B; Thøgersen, Jan; Stephansen, Anne B; Peon, Jorge; Sølling, Theis I; Keiding, Søren R

    2016-01-14

    The dynamics of 2-nitrofluorene (2-NF) in deuterated acetonitrile is studied using UV pump, IR probe femtosecond transient absorption spectroscopy. Upon excitation to the vibrationally excited S1 state, the excited-state population of 2-NF branches into two different relaxation pathways. One route leads to intersystem crossing (ISC) to the triplet manifold within a few hundred femtoseconds and the other to internal conversion (IC) to the ground state. The experiments indicate that after relaxation to the energetic minimum on S1, 2-NF undergoes internal conversion to the ground state in about 15 ps. IC within the triplet manifold is also observed as the initially populated triplet state relaxes to T1 in about 6 ps. Rotational anisotropy measurements corroborate the assignment of the transient IR frequencies and indicate a rotational diffusion time of 2-NF in the solvent of about 14 ps. The combined set of results provides a unified picture of the dynamics in photoexcited 2-NF. This to our knowledge is the first example using femtosecond vibrational spectroscopy for the study of the fundamental photoinduced processes in nitroaromatic compounds. PMID:26669456

  6. A new graphical version of STROTAB: The analysis and fitting of singlet triplet spectra of asymmetric top molecules in the prolate or oblate limits

    NASA Astrophysics Data System (ADS)

    Kodet, John; Judge, Richard H.

    2007-05-01

    .:11 913 No. of bytes in distributed program, including test data, etc.: 2 816 652 Memory required to execute with typical data: 7 Meg No of bits in a word: 16 No of processors used: 1 Has the code been vectorized or parallelized?: No No. of bytes in distributed program, including test data, etc.: ˜3.2 MB (compressed) Distribution format: zip file Additional keywords:near oblate top, bootstrap eigenvalue sorting, graphical environment, band contour Nature of physical problem: The least-squares/band contour fitting of the singlet-triplet spectra of asymmetric tops of orthorhombic symmetry using a basis set appropriate to the symmetric top limit (prolate or oblate) of the molecule in either Hund's case (a) or case (b) coupling situations. Method of solution: The calculation of the eigenvectors and eigenvalues remains unchanged from the earlier version. An option to sort the eigenvalues of the current J by fitting them to regular progressions formed from earlier J values (bootstrap method) can be used as an option in place of the existing method based on eigenvector coefficients. Reasons for the new version: The earlier version can only handle oblate tops by diagonalizing using the prolate limit. This has turned out to be unacceptable. An improved method of sorting eigenvalues under certain conditions is also needed. A graphical interface has been added to ease the use of the program. Summary of revisions: The Hamiltonian can now be constructed in a limit appropriate the representation for of the molecule. Sorting by an alternate method is now offered. Numerous graphical features have been added. Restrictions on complexity of the problem: The rotational quantum number restrictions are J⩽255 and K (or P) ⩽127. The allowed transition frequency minus the band origin frequency must be in the range of ±10 000 cm -1. Up to five decimal places may be reported. The number of observed lines is limited by the dynamic memory and the amount of disk space available. Only

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

    PubMed

    Musial, Monika; Bartlett, Rodney J

    2008-12-28

    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.

  8. Monte Carlo simulations of triplet-state photophysics for super-resolution imaging of fluorophore-labeled gold nanorods

    NASA Astrophysics Data System (ADS)

    Titus, Eric J.; Blythe, Karole L.; Willets, Katherine A.

    2015-08-01

    Super-resolution imaging has previously been used to identify the position of individual fluorescently-labeled DNA molecules bound to the surface of gold nanorods. In order to isolate and fit emission from individual fluorophores, a stochastic photoswitching technique based on shelving the fluorophores into triplet states is used. However, the reconstructed super-resolution images of the fluorescently-labeled gold nanorods are consistently smaller than the expected size of the gold nanorod supports. Here, Monte Carlo simulations are used to probe how smaller-than-expected reconstructed images may be obtained by simultaneous emission events based on short triplet state lifetimes and/or a high density of fluorescently-labeled DNA on the gold nanorod surface.

  9. Zero-field splitting of the lowest excited triplet states of C(60) and C(70) and benzene.

    PubMed

    van Gastel, Maurice

    2010-10-14

    The electronic structure of the lowest excited triplet states of C(60) and C(70) are characterized by a magnetic interaction between the unpaired electrons for which the zero-field-splitting parameter D is negative for the former and positive for the latter molecule. The sign of D has so far been qualitatively understood, and its magnitude has been found to critically depend on the degree of delocalization of the singly occupied molecular orbitals. In this contribution, the effect of spin polarization to the zero-field-splitting parameters of the fullerenes is evaluated, the inclusion of which results in quantitative agreement between the experimental and calculated D values. The direct spin-spin contribution is found to be dominant for both molecules. For C(60), a significant contribution of 20% of the total zero-field splitting has been found to derive from spin polarization. The physical reason for the sign difference of D for C(60) and C(70) is traced back to the relative phases of the local p(z) orbitals of adjacent carbon atoms near the equatorial plane in both singly occupied molecular orbitals. These relative phases differ for C(60) and C(70), because C(70) has an additional set of ten carbon atoms in its equatorial plane as compared to C(60). Additionally, the triplet wave function of C(70) is found to contain significant multireference character. In order to evaluate the effect of spin polarization in multireference systems, the zero-field-splitting parameters of the lowest triplet state of benzene have been evaluated in an illustrative and insightful calculation as well. Though this prototypical molecule is much smaller than C(60) and C(70), the electronic structure of its lowest excited triplet state is also of multireference character. For benzene, 18% of the total zero-field splitting arises from spin polarization.

  10. The role played by some factors of intramolecular interaction in nonradiative deactivation of the lowest triplet state of octachlorodibenzo- p-dioxin

    NASA Astrophysics Data System (ADS)

    Gastilovich, E. A.; Klimenko, V. G.; Volkova, L. V.; Nurmukhametov, R. N.

    2012-11-01

    We have studied how intramolecular interactions, such as vibronically induced spin-orbit (VISO) and nonadiabatic interactions, which are governed by different structural elements of the octachlorodibenzo- p-dioxin (OCDD) molecule, affect the deactivation of its lowest triplet state. In the nonadiabatic approximation, taking into account out-of-plane vibrational modes as promoting ones, we have estimated the values of rate constant K {dg/s} of the nonradiative energy deactivation of in-plane triplet sublevels ( s = z, y) of the triplet state of the OCDD molecule.

  11. 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.

  12. Nonradiative deactivation of the lowest triplet state of tetrachlorodibenzo- p-dioxin

    NASA Astrophysics Data System (ADS)

    Gastilovich, E. A.; Klimenko, V. G.; Volkova, L. V.; Nurmukhametov, R. N.

    2014-03-01

    In the nonadiabatic approximation, we have studied how the shape of promoting out-of-plane vibrational modes and vibronically induced spin-orbit interactions in structural elements of the 2,3,7,8-tetrachlorodibenzo- p-dioxin molecule affect the energy degradation rate constants K {dg/ s } of triplet T {1/ s } sublevels.

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

    PubMed Central

    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. Images FIGURE 12 PMID:8994622

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

    PubMed

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

    2011-11-21

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

  15. Spin—lattice relaxation in a guest triplet state is induced by proton tunneling in a benzoic acid host crystal

    NASA Astrophysics Data System (ADS)

    Chaudhuri, D.; Schlyer, B. D.; Maki, A. H.

    1991-03-01

    Spin—lattice relaxation (SLR) of the triplet state of pentacene-6,13-quinone (PQ) in n-C 11H 24, and as a guest impurity in benzoic acid, BA- h2 and the acid deuterated host, BA- d2, has been measured at temperatures near 4 K. Enhanced SLR in the BA hosts relative to n-C 11H 24 is a thermally activated process which we attribute to a phonon-assisted tunneling transition between local BA tautomer states.

  16. 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

  17. 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

  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. 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.

  20. Inversion of 4-methoxybenzophenone triplet in aqueous solutions.

    PubMed

    Boscá, Francisco; Cosa, Gonzalo; Miranda, Miguel A; Scaiano, J C

    2002-09-01

    The triplet state of 4-methoxybenzophenone (4-MBP) has been investigated by laser flash photolysis and emission techniques in several solvents. In non-polar cyclohexane, 4-MBP triplet has an (n,pi*) configuration with the typical triplet-triplet absorption spectrum of benzophenone (lambda(max) ca. 525 nm). However, due to the proximity of the two lowest triplet states of different configuration, some unusual features are observed in polar solvents. Thus, 4-MBP shows in aqueous solutions a transient absorption spectrum with lambda(max) at 450 and 680 nm, which can be attributed to a T1 (pi,pi*) state. Further, transient absorption spectra due to T1 (n,pi*) and T2 (pi,pi*) being simultaneously populated are observed upon laser excitation of 4-MBP in polar solvents such as acetonitrile or methanol. The triplet state inversion (n,pi* to pi,pi*) is also detected by the measurement of triplet quenching rate constants by 1,4-cyclohexadiene (a good hydrogen donor) in acetonitrile and water (kH ca. 2 x 10(8) and 5 x 10(5) M(-1) s(-1), respectively) and by the determination of room-temperature phosphorescence (the emission quantum yield at room-temperature decreases from 0.004 in acetonitrile to less than 1 x 10(-6) in water). Further, the energy of the 4-MBP triplet state is ca. 288 kJ mol(-1) both in polar and non-polar organic solvents, while in water it drops to 275 kJ mol(-1). The photophysical properties of 4-MBP are compared with those of 4-aminobenzophenone (4-ABP), which also possesses an electron-donating group. In polar organic solvents such as acetonitrile, the transient absorption spectrum and the quenching rate constant of hydrogen abstraction for triplet 4-ABP are practically the same as those obtained for 4-MBP in aqueous solutions. On the other hand, a small T2 (pi,pi*) contribution is observed in the triplet-triplet absorption spectrum of 4-ABP in cyclohexane.

  1. 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

  2. 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

  3. 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.

  4. Control of ferromagnetic and antiferromagnetic couplings in a galvinoxyl triplet chrysene encounter complex through solvent polarity

    NASA Astrophysics Data System (ADS)

    Kawai, Akio; Watanabe, Yasuyuki; Shibuya, Kazuhiko

    2003-04-01

    Energy difference, J, between the quartet and doublet spin states of a galvinoxyl radical-triplet chrysene pair as an encounter complex in solution was investigated by measuring chemically induced dynamic electron polarization (CIDEP) of galvinoxyl with a time-resolved ESR (TR-ESR) method. All the TR-ESR spectra of galvinoxyl show net type CIDEP signals due to doublet-triplet magnetic interactions. The CIDEP phase switches from absorption in non-polar solvent to emission in polar solvent. The signals were analyzed on the basis of the radical-triplet pair mechanism (RTPM) for CIDEP creation, the results of which indicate that galvinoxyl-triplet chrysene pairs show ferromagnetic and antiferromagnetic couplings in non-polar and polar solvents, respectively. This solvent polarity-controlled switching of magnetic coupling in the galvinoxyl-triplet chrysene pair was interpreted by introducing the effect of intermolecular charge transfer interaction on the J value.

  5. Spin-triplet paired state induced by Hund's rule coupling and correlations: a fully statistically consistent Gutzwiller approach.

    PubMed

    Spałek, J; Zegrodnik, M

    2013-10-30

    The intrasite and intersite spin-triplet pairing gaps induced by interband Hund's rule coupling and their correlations are analyzed in the doubly degenerate Hubbard Hamiltonian. To include the effect of correlations, the statistically consistent Gutzwiller approximation is used. In this approach the consistency means that the averages calculated from the self-consistent equations and those determined variationally coincide with each other. Emphasis is put on the solution for which the average particle number is conserved when carrying out the Gutzwiller projection. This method leads to a stable equal-spin paired state in the so-called repulsive interactions limit (U > 3J) in the regime of moderate correlations. The interband hybridization introduces an inequivalence of the bands which, above a critical magnitude, suppresses the paired state due to both the Fermi-wavevector mismatch for the Cooper pair and the interband hopping allowed by the Pauli principle.

  6. Singlet Oxygen and Dye-Triplet-State Quenching in Solid-State Dye Lasers Consisting of Pyrromethene 567 Doped Poly(Methyl Methacrylate)

    NASA Astrophysics Data System (ADS)

    Ahmad, Mohammad; Rahn, Mark D.; King, Terence A.

    1999-10-01

    Solid-state dye lasers based on poly(methyl methacrylate) (PMMA) doped with Pyrromethene 567 dye (P567) have been investigated. The preparation techniques employed provided high photostability and laser damage threshold for P567 in pure PMMA with 270,000 pulses emitted before the conversion efficiency fell to half its initial value for a pump fluence of 0.16 J cm 2 . When PMMA was modified with 1,4-diazobicyclo 2,2,2 octane singlet oxygen quencher, the longevity increased to 550,000 pulses, corresponding to a normalized photostability of 270 GJ mol 1 . Modification of PMMA with a triplet quencher (perylene) yielded no improvement, but in ethanol solutions both additives enhanced photostability. It is possible that in PMMA, stabilization by means of triplet quenching that depends on dye diffusion is prevented but that stabilization by means of singlet oxygen quenching that depends on the faster oxygen diffusion rate will succeed.

  7. 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.

  8. 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

  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. Photoemission spectra of charge density wave states in cuprates

    NASA Astrophysics Data System (ADS)

    Tu, Wei-Lin; Chen, Peng-Jen; Lee, Ting-Kuo

    Angle-resolved photoemission spectroscopy(ARPES) experiments have reported many exotic properties of cuprates, such as Fermi arc at normal state, two gaps at superconducting state and particle-hole asymmetry at the antinodal direction. On the other hand, a number of inhomogeneous states or so-called charge density waves(CDW) states have also been discovered in cuprates by many experimental groups. The relation between these CDW states and ARPES spectra is unclear. With the help of Gutzwiller projected mean-field theory, we can reproduce the quasiparticle spectra in momentum space. The spectra show strong correspondence to the experimental data with afore-mentioned exotic features in it.

  11. 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.

  12. Observations and theoretical analysis of highly excited singlet and triplet states of cadmium

    NASA Astrophysics Data System (ADS)

    Vidolova-Angelova, E.; Baharis, C.; Roupakas, G.; Kompitsas, M.

    1996-06-01

    We have recorded the 0953-4075/29/12/010/img7 - 50) bound Rydberg spectrum of cadmium. We have fully resolved the multiplet up to n = 19 and partially up to n = 24. Furthermore, we have observed the odd singlet and triplet 5sn f Rydberg series for n = 10 - 22 and n = 4 - 21, respectively. We have applied two- and three-step laser schemes to excite Cd vapour in a heat pipe-like oven which was operated as a thermionic diode for detection. Theoretical calculations were performed for the energies of the 5sn p and 5sn f series using perturbation theory with a zero-order model approximation. There is a good agreement between theoretical and experimental results for the 5sn p series, the deviation decreasing with n and being 1 - 2 0953-4075/29/12/010/img8 for n = 50. The agreement for the 5sn f is satisfactory. From the quantum defect of the 5sn f series we approximate a value of the effective dipole polarizability of the 0953-4075/29/12/010/img9 ion of 0953-4075/29/12/010/img10 in units of the Bohr radius.

  13. Phosphorescence maxima and triplet state lifetimes of NAD+ and epsilon-NAD+ in ternary complexes with horse liver alcohol dehydrogenase.

    PubMed

    Rousslang, K; Allen, L; Ross, J B

    1989-02-01

    This paper describes the phosphorescence emission and decay times of NAD+ and its fluorescent etheno derivative, epsilon-NAD+, in the pyrazole ternary complex with horse liver alcohol dehydrogenase (ADH). We show that the epsilon-NAD+ triplet state, as well as the tryptophan triplet state, can be utilized to monitor the coenzyme-enzyme interaction. The decays of NAD+ and AMP are single exponential, and the lifetimes are the same within experimental error. The phosphorescence lifetimes, evaluated as single exponentials, are slightly shorter in epsilon-NAD+ than they are in epsilon-AMP. Whereas the decay of epsilon-AMP was adequately fit by a single exponential with a time constant of very close to 0.5 s, it was necessary to fit the decay of epsilon-NAD+ to a double exponential. Ternary complexes with NAD+ excited at 297 nm exhibit decay kinetics nearly identical to those of ADH by itself. On the other hand, when excitation of the epsilon-NAD+ ternary complex is provided at 313 nm, where there is very little absorption by either tryptophan residue, the decay law of the ternary complex is similar to that of epsilon-NAD+ in solution. Our results demonstrate that NAD+ and epsilon-NAD+ quench tryptophan phosphorescence in ADH. Normalizing the phosphorescence intensity to the 0-0 vibronic band assigned to Trp-15 (blue-edge), we calculate a 21% decrease in the phosphorescence associated with Trp-314 at stoichiometric saturation of the coenzyme binding sites with NAD+ in the ternary complex. When the active sites are saturated with epsilon-NAD+, the relative phosphorescence due to Trp-314 decreases by 63%.(ABSTRACT TRUNCATED AT 250 WORDS)

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

    PubMed

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

    2012-04-01

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

  15. 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.

  16. Toward the Understanding of the Photophysics and Photochemistry of 1-Nitronaphthalene under Solar Radiation: The First Theoretical Evidence of a Photodegradation Intramolecular Rearrangement Mechanism Involving the Triplet States.

    PubMed

    Giussani, Angelo

    2014-09-01

    1-Nitronaphthalene belongs to the class of nitrated polycyclic aromatic hydrocarbons, and constitutes an atmospheric pollutant commonly found in urban environments due to its production during incomplete combustions. On the basis of CASPT2//CASSCF quantum chemical calculations, the photophysics and photochemistry of the system under solar exposure have for the first time been studied. According to the characteristics of the incident radiation (either UVA or UVB, both present in the portion of the solar spectrum reaching the earth), a different excited state will be mainly populated. In both cases, the main decay path undertaken by the corresponding bright state leads to an efficient intersystem crossing process toward the (3)(πOπ*) triplet excited state. The population of the triplet manifold is then identified as the primary photoinduced process in the title molecule, not only after UVA interaction but also under UVB exposure. From the (3)(πOπ*) state, the system can either decay in a radiationless manner to the original ground state minimum, or undergo a photodegradation process mediated by the presence of an accessible singlet-triplet crossing region characterized by the formation of a oxaziridine ring. The determination of such a photodegradation path constitutes the first theoretical evidence supporting the hypothesis formulated almost 50 years ago in the seminal work of Chapman et al. (J. Am. Chem. Soc. 1966, 88, 5550), according to which the photolysis undertaken by nitrated polycyclic aromatic hydrocarbons proceeds through an intramolecular rearrangement mechanism, here characterized on the triplet manifold.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  18. Theory of triplet optical absorption in oligoacenes: From naphthalene to heptacene

    SciTech Connect

    Chakraborty, Himanshu Shukla, Alok

    2014-10-28

    In this paper, we present a detailed theory of the triplet states of oligoacenes containing up to seven rings, i.e., starting from naphthalene all the way up to heptacene. In particular, we present results on the optical absorption from the first triplet excited state 1{sup 3}B{sub 2u}{sup +} of these oligomers, computed using the Pariser-Parr-Pople model Hamiltonian, and a correlated electron approach employing the configuration-interaction methodology at various levels. Excitation energies of various triplets states obtained by our calculations are in good agreement with the experimental results, where available. The computed triplet spectra of oligoacenes exhibits rich structure dominated by two absorption peaks of high intensities, which are well separated in energy, and are caused by photons polarized along the conjugation direction. This prediction of ours can be tested in future experiments performed on oriented samples of oligoacenes.

  19. Photophysical properties of some methylindoles and studies on quenching reactions in their excited singlet and triplet states in presence of the electron acceptor 2-nitrofluorene at 296 K as well as at 77 K

    NASA Astrophysics Data System (ADS)

    Sinha, S.; De, R.; Ganguly, T.

    1998-01-01

    Electronic absorption, steady state and time resolved, in the domain of nanosecond order, luminescence techniques were employed to study the photophysical properties of some electron donors methylindoles, e.g. 1-methylindole (1MI), 2-methylindole (2MI), 3-methylindole (3MI) and 5-methylindole (5MI) in nonpolar and polar environments at 296 K and in ethanol (EtOH) rigid glassy matrix at 77 K in the presence of electron acceptor 2-nitrofluorene (2NF). It has been proposed that at room temperature and in polar acetonitrile (ACN) solvent, MI (1, 2 or 3) emission originates mainly from the closely lying lowest excited states S 1 ( 1L b), S 2 ( 1L a) and the charge transfer (CT) exciplex state which is formed due to solute-highly polar solvent ACN interaction. This CT state has its origin in 1L a. The room temperature fluorescence quenchings of the MI donors in presence of acceptor 2NF are found to be mainly due to photoinduced electron transfer (ET), excitational energy transfer and transient quenching processes. Out of the three processes Förster's long range energy transfer seems to be the most dominant one. At 77 K singlet-singlet and triplet-triplet energy transfer processes seem to be responsible for the observed quenching in fluorescence and phosphorescence spectra of the donor molecules in presence of the acceptor 2NF.

  20. Triplet-Triplet Energy Transfer Study in Hydrogen Bonding Systems.

    PubMed

    Wang, Zhijia; Zhao, Jianzhang; Guo, Song

    2015-01-01

    The 2,6-diiodoBodipy-styrylBodipy hydrogen bonding system was prepared to study the effect of hydrogen bonding on the triplet-triplet-energy-transfer (TTET) process. 2,6-DiiodoBodipy linked with N-acetyl-2,6-diaminopyridine (D-2) was used as the triplet energy donor, and the styrylBodipy connected with thymine (A-1) was used as triplet energy acceptor, thus the TTET process was established upon photoexcitation. The photophysical processes of the hydrogen bonding system were studied with steady-state UV-vis absorption spectroscopy, fluorescence spectroscopy, fluorescence lifetime measurement and nanosecond time-resolved transient absorption spectroscopies. The TTET of the intramolecular/hydrogen bonding/intermolecular systems were compared through nanosecond transient absorption spectroscopy. The TTET process of the hydrogen bonding system is faster and more efficient (kTTET = 6.9 × 10(4) s(-1), ΦTTET = 94.0%) than intermolecular triplet energy transfer (kTTET = 6.0 × 10(4) s(-1), ΦTTET = 90.9%), but slower and less efficient than intramolecular triplet energy transfer (kTTET > 10(8) s(-1)). These results are valuable for designing self-assembly triplet photosensitizers and for the study of the TTET process of hydrogen bonding systems.

  1. 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

  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. 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

  5. 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

  6. 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.

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

    PubMed

    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

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. Spin-sublevel properties of the ππ * triplet state of 2,2'-bipyridine. Is the out-of-plane component most emissive?

    NASA Astrophysics Data System (ADS)

    Okabe, Noriyuki; Ikeyama, Takeshi; Azumi, Tohru

    1990-01-01

    Total ( ku) and relative radiative ( kur) decay rate constants of the spin sublevels of the lowest excited triplet state of 2,2'-bipyridine were examined by ODMR (optical detection of magnetic resonance) methods. Contrary to the report of Suisalu et al., the out-of-plane sublevel is the least emissive as is usual for π-aromatic molecules. A possible cause of the difference in the present and the previous results is discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  14. Nonclassical properties of coherent states and excited coherent states for continuous spectra

    NASA Astrophysics Data System (ADS)

    Honarasa, G. R.; Tavassoly, M. K.; Hatami, M.; Roknizadeh, R.

    2011-02-01

    Based on the definition of coherent states for continuous spectra and analogous to photon-added coherent states for discrete spectra, we introduce the excited coherent states for continuous spectra. It is shown that the main axioms of Gazeau-Klauder coherent states will be satisfied, properly. Nonclassical properties and quantum statistics of coherent states, as well as the introduced excited coherent states, are discussed. In particular, through the study of quadrature squeezing and amplitude-squared squeezing, it will be observed that both classes of the above states can be classified in the intelligent states category.

  15. a Quantum Chemical Study of Familiar and Exotic Low-Lying Singlet and Triplet States of CH2, CF2, and Chf

    NASA Astrophysics Data System (ADS)

    Xu, Lu; Woon, D. E.; Dunning, T. H., Jr.

    2010-06-01

    High level MRCI and RCCSD(T) calculations using triple and quadruple zeta quality correlation consistent basis sets were used to study the low-lying singlet and triplet states of CH2, CF2, and CHF. The bonding in carbon was found to be very similar to that of sulfur, where there is also a competition between states that form through normal covalent bonding and recoupled pair bonding. The recoupled pair bonding model was used to investigate these states systematically to see how closely they resemble the behavior of SF2, which has a 1A1 ground state and 3B1 and 3A2 excited states. In addition to accounting for the separations and ordering of the lowest singlet and triplet states of each species, the less-studied 3A2 states of CH2 and CF2 and the 3A^" state of CHF were investigated and compared to gain insight into the underlying reasons for the energetic and bonding differences between these species. Interestingly, the 3A2 state of CH2 is a cyclic structure, the 3A2 state of CF2 is bent but not cyclic (resembling the same state of SF_2), and the analogous minimum structure on the 3A^" surface of CHF is a C---HF complex.

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

    PubMed

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

    2015-04-21

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

  17. 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.

  18. Efficient enhancement of the visible-light absorption of cyclometalated Ir(III) complexes triplet photosensitizers with Bodipy and applications in photooxidation and triplet-triplet annihilation upconversion.

    PubMed

    Sun, Jifu; Zhong, Fangfang; Yi, Xiuyu; Zhao, Jianzhang

    2013-06-01

    We report molecular designing strategies to enhance the effective visible-light absorption of cyclometalated Ir(III) complexes. Cationic cyclometalated Ir(III) complexes were prepared in which boron-dipyrromethene (Bodipy) units were attached to the 2,2'-bipyridine (bpy) ligand via -C≡C- bonds at either the meso-phenyl (Ir-2) or 2 position of the π core of Bodipy (Ir-3). For the first time the effect of π conjugating (Ir-3) or tethering (Ir-2) of a light-harvesting chromophore to the coordination center on the photophysical properties was compared in detail. Ir(ppy)2(bpy) (Ir-1; ppy = 2-phenylpyridine) was used as model complex, which gives the typical weak absorption in visible range (ε < 4790 M(-1) cm(-1) in region > 400 nm). Ir-2 and Ir-3 showed much stronger absorption in the visible range (ε = 71,400 M(-1) cm(-1) at 499 nm and 83,000 M(-1) cm(-1) at 527 nm, respectively). Room-temperature phosphorescence was only observed for Ir-1 (λ(em) = 590 nm) and Ir-3 (λ(em) = 742 nm). Ir-3 gives RT phosphorescence of the Bodipy unit. On the basis of the 77 K emission spectra, nanosecond transient absorption spectra, and spin density analysis, we proposed that Bodipy-localized long-lived triplet excited states were populated for Ir-2 (τT = 23.7 μs) and Ir-3 (87.2 μs). Ir-1 gives a much shorter triplet-state lifetime (0.35 μs). Complexes were used as singlet oxygen ((1)O2) photosensitizers in photooxidation. The (1)O2 quantum yield of Ir-3 (ΦΔ = 0.97) is ca. 2-fold of Ir-2 (ΦΔ = 0.52). Complexes were also used as triplet photosensitizer for TTA upconversion; upconversion quantum yields of 1.2% and 2.8% were observed for Ir-2 and Ir-3, respectively. Our results proved that the strong absorption of visible light of Ir-2 failed to enhance production of a triplet excited state. These results are useful for designing transition metal complexes that show effective strong visible-light absorption and long-lived triplet excited states, which can be used as ideal

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. Diphotons from electroweak triplet-singlet mixing

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. Magnetic Field Effects on Triplet-Triplet Annihilation in Solutions: Modulation of Visible/NIR Luminescence.

    PubMed

    Mani, Tomoyasu; Vinogradov, Sergei A

    2013-08-01

    Photon upconversion based on sensitized triplet-triplet annihilation (TTA) presents interest for such areas as photovoltaics and imaging. Usually energy upconversion is observed as p-type delayed fluorescence from molecules whose triplet states are populated via energy transfer from a suitable triplet donor, followed by TTA. Magnetic field effects (MFE) on delayed fluorescence in molecular crystals are well known; however, there exist only a few examples of MFE on TTA in solutions, and all of them are limited to UV-emitting materials. Here we present MFE on TTA-mediated visible and near infrared (NIR) emission, sensitized by far-red absorbing metalloporphyrins in solutions at room temperature. In addition to visible delayed fluorescence from annihilator, we also observed NIR emission from the sensitizer, occurring as a result of triplet-triplet energy transfer back from annihilator, termed "delayed phosphorescence". This emission also exhibits MFE, but opposite in sign to the annihilator fluorescence.

  16. Magnetic Field Effects on Triplet-Triplet Annihilation in Solutions: Modulation of Visible/NIR Luminescence

    PubMed Central

    Mani, Tomoyasu; Vinogradov, Sergei A.

    2013-01-01

    Photon upconversion based on sensitized triplet-triplet annihilation (TTA) presents interest for such areas as photovoltaics and imaging. Usually energy upconversion is observed as p-type delayed fluorescence from molecules whose triplet states are populated via energy transfer from a suitable triplet donor, followed by TTA. Magnetic field effects (MFE) on delayed fluorescence in molecular crystals are well known; however, there exist only a few examples of MFE on TTA in solutions, and all of them are limited to UV-emitting materials. Here we present MFE on TTA-mediated visible and near infrared (NIR) emission, sensitized by far-red absorbing metalloporphyrins in solutions at room temperature. In addition to visible delayed fluorescence from annihilator, we also observed NIR emission from the sensitizer, occurring as a result of triplet-triplet energy transfer back from annihilator, termed “delayed phosphorescence”. This emission also exhibits MFE, but opposite in sign to the annihilator fluorescence. PMID:24143268

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  18. Singlet and triplet potentials of the ground-state atom pair Rb + Cs studied by Fourier-transform spectroscopy

    SciTech Connect

    Docenko, O.; Tamanis, M.; Ferber, R.; Knoeckel, H.; Tiemann, E.

    2011-05-15

    A comprehensive study of the X {sup 1}{Sigma}{sup +} and a {sup 3}{Sigma}{sup +} electronic states of the Rb and Cs atom pair in RbCs is presented. Abundant spectroscopic data for the {sup 85}Rb{sup 133}Cs and {sup 87}Rb{sup 133}Cs isotopologues were obtained from Fourier-transform spectra of laser-induced fluorescence (LIF) from the B {sup 1}{Pi} and (4){sup 1}{Sigma}{sup +} states to the a {sup 3}{Sigma}{sup +} (4549 transitions) and X {sup 1}{Sigma}{sup +} (15 709 transitions) states. The X {sup 1}{Sigma}{sup +} state data were complemented by about 15 500 transitions obtained by Fellows et al.[J. Mol. Spectrosc. 197, 19 (1999)]. LIF progressions to the a {sup 3}{Sigma}{sup +} state range from v{sub a}=0 to 37, reaching an outer turning point at 15.97 A. For the X {sup 1}{Sigma}{sup +} state, by analyzing LIF from the shelflike (4){sup 1}{Sigma}{sup +}, the data are extended from v{sub x}=119 as observed in the above-cited paper to v{sub x}=129, extending the outer turning point from 10.7 to 17.55 A. From these data, potential energy curves were constructed simultaneously for both hyperfine coupled states X {sup 1}{Sigma}{sup +} and a {sup 3}{Sigma}{sup +} in a coupled-channels fitting routine. This allowed us to accurately model the potential close to the Rb(5s) + Cs(6s) atom-pair asymptote, which is required to simulate cold collision processes and to analyze the Feshbach resonances observed for {sup 87}Rb{sup 133}Cs by Pilch et al.[Phys. Rev. A 79, 042718 (2009)]. Dissociation energies were determined for the X {sup 1}{Sigma}{sup +} state as D{sub e}=3836.373(40) cm{sup -1} and for the a {sup 3}{Sigma}{sup +} state as D{sub e}=259.341(30) cm{sup -1}.

  19. Infrared absorption spectra of various doping states in cuprate superconductors

    SciTech Connect

    Yonemitsu, K.; Bishop, A.R.; Lorenzana, J.

    1992-02-01

    Doping states in a two-dimensional three-band extended Peierls-Hubbard model was investigated within inhomogeneous Hartree-Fock and random phase approximation. They are very sensitive to small changes of interaction parameters and their distinct vibrational and optical absorption spectra can be used to identify different doping states. For electronic parameters relevant to cuprate superconductors, as intersite electron-phonon interaction strength increases, the doping state changes from a Zhang-Rice state to a covalent molecular singlet state accompanied by local quenching of the Cu magnetic moment and large local lattice distortion in an otherwise undistorted antiferromagnetic background. In a region where both intersite electron-phonon interaction and on-site electron-electron repulsion are large, we obtain new stable global phases including a bond-order-wave state and a mixed state of spin-Peierls bonds and antiferromagnetic Cu spins, as well as many metastable states. Doping in the bond-order-wave region induces separation of spin and charge. 9 refs.

  20. Infrared absorption spectra of various doping states in cuprate superconductors

    SciTech Connect

    Yonemitsu, K.; Bishop, A.R. ); Lorenzana, J. )

    1992-01-01

    Doping states in a two-dimensional three-band extended Peierls-Hubbard model was investigated within inhomogeneous Hartree-Fock and random phase approximation. They are very sensitive to small changes of interaction parameters and their distinct vibrational and optical absorption spectra can be used to identify different doping states. For electronic parameters relevant to cuprate superconductors, as intersite electron-phonon interaction strength increases, the doping state changes from a Zhang-Rice state to a covalent molecular singlet state accompanied by local quenching of the Cu magnetic moment and large local lattice distortion in an otherwise undistorted antiferromagnetic background. In a region where both intersite electron-phonon interaction and on-site electron-electron repulsion are large, we obtain new stable global phases including a bond-order-wave state and a mixed state of spin-Peierls bonds and antiferromagnetic Cu spins, as well as many metastable states. Doping in the bond-order-wave region induces separation of spin and charge. 9 refs.

  1. Crossing behavior of the singlet and triplet State of the negatively charged magneto-exciton in a GaAs/AlGaAs quantum well

    SciTech Connect

    MUNTEANU,F.M.; KIM,YONGMIN; PERRY,C.H.; RICKEL,D.G.; SIMMONS,JERRY A.; RENO,JOHN L.

    2000-01-27

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

  2. Single-shot readout and relaxation of singlet and triplet states in exchange-coupled 31P electron spins in silicon.

    PubMed

    Dehollain, Juan P; Muhonen, Juha T; Tan, Kuan Y; Saraiva, Andre; Jamieson, David N; Dzurak, Andrew S; Morello, Andrea

    2014-06-13

    We present the experimental observation of a large exchange coupling J ≈ 300 μeV between two (31)P electron spin qubits in silicon. The singlet and triplet states of the coupled spins are monitored in real time by a single-electron transistor, which detects ionization from tunnel-rate-dependent processes in the coupled spin system, yielding single-shot readout fidelities above 95%. The triplet to singlet relaxation time T(1) ≈ 4 ms at zero magnetic field agrees with the theoretical prediction for J-coupled 31P dimers in silicon. The time evolution of the two-electron state populations gives further insight into the valley-orbit eigenstates of the donor dimer, valley selection rules and relaxation rates, and the role of hyperfine interactions. These results pave the way to the realization of two-qubit quantum logic gates with spins in silicon and highlight the necessity to adopt gating schemes compatible with weak J-coupling strengths. PMID:24972221

  3. 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.

  4. Single-shot readout and relaxation of singlet and triplet states in exchange-coupled 31P electron spins in silicon.

    PubMed

    Dehollain, Juan P; Muhonen, Juha T; Tan, Kuan Y; Saraiva, Andre; Jamieson, David N; Dzurak, Andrew S; Morello, Andrea

    2014-06-13

    We present the experimental observation of a large exchange coupling J ≈ 300 μeV between two (31)P electron spin qubits in silicon. The singlet and triplet states of the coupled spins are monitored in real time by a single-electron transistor, which detects ionization from tunnel-rate-dependent processes in the coupled spin system, yielding single-shot readout fidelities above 95%. The triplet to singlet relaxation time T(1) ≈ 4 ms at zero magnetic field agrees with the theoretical prediction for J-coupled 31P dimers in silicon. The time evolution of the two-electron state populations gives further insight into the valley-orbit eigenstates of the donor dimer, valley selection rules and relaxation rates, and the role of hyperfine interactions. These results pave the way to the realization of two-qubit quantum logic gates with spins in silicon and highlight the necessity to adopt gating schemes compatible with weak J-coupling strengths.

  5. Narrow chaotic compound autoionizing states in atomic spectra

    SciTech Connect

    Flambaum, V.V.; Gribakina, A.A.; Gribakin, G.F.

    1996-09-01

    Simultaneous excitation of several valence electrons in atoms gives rise to a dense spectrum of compound autoionizing states (AIS). These states are almost chaotic superpositions of large numbers of many-electron basis states built of single-electron orbitals. The mean level spacing {ital D} between such states is very small (e.g., {ital D}{lt}0.01 eV for the numerical example of {ital J}{sup {pi}}=4{sup {minus}} states of Ce just above the ionization threshold). The autoionization widths of these states estimated by perturbations, {gamma}=2{pi}{vert_bar}{ital W}{vert_bar}{sup 2}, where {ital W} is the Coulomb matrix element coupling the AIS to the continuum, are also small, but comparable with {ital D} in magnitude: {gamma}{approximately}{ital D}. Hence the nonperturbative interaction of AIS with each other via the continuum is very essential. It suppresses greatly the widths of the autoionizing resonances ({Gamma}{approx_equal}{ital D}{sup 2}/3{gamma}{lt}{ital D}), and leads to the emergence of a {open_quote}{open_quote}collective{close_quote}{close_quote} doorway state which accumulates a large share of the total width. This state is in essence a modified single-particle continuum decoupled from the resonances due to its large width. Narrow compound AIS should be a common feature of atomic spectra at energies sufficient for excitation of several electrons above the ground-state configuration. The narrow resonances can be observed as peaks in the photoabsorption, or, in electron-ion scattering, as Fano-type profiles on the background provided by the wide doorway-state resonance. It is also shown that the statistics of electromagnetic and autoionization amplitudes involving compound states are close to Gaussian. {copyright} {ital 1996 The American Physical Society.}

  6. 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).

  7. Electronic states and spectra of BiS

    NASA Astrophysics Data System (ADS)

    Setzer, K. D.; Meinecke, F.; Fink, E. H.

    2009-11-01

    NIR/VIS emission spectra of BiS were measured in the 5800-25 000 cm -1 region with a Fourier-transform spectrometer. BiS was produced by reaction of bismuth and sulfur vapor and excited by energy transfer from metastable oxygen O 2( a1Δ g) in a fast-flow system. The spectrum of BiS was found to be closely related to that of the previously studied BiO radical [O. Shestakov et al., J. Mol. Spectrosc. 190 (1998) 28-77]. Five transitions connecting the Ω-components of the first three excited states, A4Π( A13/2, A21/2), B2Π( B11/2), and C4Σ -( C11/2, C23/2), with the components of the strongly split ground state, X2Π( X11/2, X23/2, have been observed and analyzed.

  8. Metal-to-Ligand Charge-Transfer Emissions of Ruthenium(II) Pentaammine Complexes with Monodentate Aromatic Acceptor Ligands and Distortion Patterns of their Lowest Energy Triplet Excited States.

    PubMed

    Tsai, Chia Nung; Mazumder, Shivnath; Zhang, Xiu Zhu; Schlegel, H Bernhard; Chen, Yuan Jang; Endicott, John F

    2015-09-01

    This is the first report of the 77 K triplet metal-to-ligand charge-transfer ((3)MLCT) emission spectra of pentaammine-MDA-ruthenium(II) ([Ru(NH3)5(MDA)](2+)) complexes, where MDA is a monodentate aromatic ligand. The emission spectra of these complexes and of the related trans-[Ru(NH3)4(MDA) (MDA')](2+) complexes are closely related, and their emission intensities are very weak. Density functional theory (DFT) calculations indicate that the energies of the lowest (3)MLCT excited states of Ru-MDA complexes are either similar to or lower than those of the lowest energy metal-centered excited states ((3)MC(X(Y))), that the barrier to internal conversion at 77 K is large compared to kBT, and that the (3)MC(X(Y)) excited states are weakly bound. The [Ru(NH3)5py](2+) complex is an exception to the general pattern: emission has been observed for the [Ru(ND3)5(d5-py)](2+) complex, but its lifetime is apparently very short. DFT modeling indicates that the excited state distortions of the different (3)MC excited states are very large and are in both Ru-ligand bonds along a single Cartesian axis for each different (3)MC excited state, nominally resulting in (3)MC(X(Y)), (3)MC((X)Y), and (3)MC(Z) lowest energy metal-centered states. The (3)MC(X(Y)) and (3)MC((X)Y) states appear to be the pseudo-Jahn-Teller distorted components of a (3)MC((XY)) state. The (3)MC(X(Y)) states are distorted up to 0.5 Å in each H3N-Ru-NH3 bond along a single Cartesian axis in the pentaammine and trans-tetraammine complexes, whereas the (3)MC(Z) states are found to be dissociative. DFT modeling of the (3)MLCT excited state of [Ru(NH3)5(py)](2+) indicates that the Ru center has a spin density of 1.24 at the (3)MLCT energy minimum and that the (3)MLCT → (3)MC(Z) crossing is smooth with a very small barrier (<0.5 kcal/mol) along the D3N-Ru-py distortion coordinate, implying strong (3)MLCT/(3)MC excited state configurational mixing. Furthermore, the DFT modeling indicates that the long

  9. Triplet absorption spectroscopy and electromagnetically induced transparency

    NASA Astrophysics Data System (ADS)

    Ghafoor, F.; Nazmitdinov, R. G.

    2016-09-01

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

  10. 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.

  11. Properties of triplet-excited [N]cycloparaphenylenes (N = 8-12): excitation energies lower than those of linear oligomers and polymers.

    PubMed

    Fujitsuka, Mamoru; Lu, Chao; Iwamoto, Takahiro; Kayahara, Eiichi; Yamago, Shigeru; Majima, Tetsuro

    2014-06-26

    Cycloparaphenylenes (CPPs), a class of hoop-shaped conjugated macrocycles, have attracted the attention of researchers in various fields because of their interesting properties. Although their properties in the singlet-excited state have been reported, there is no systematic information on the triplet-excited state. In the present study, the properties of triplet-excited [n]CPP (n = 8-12, where n denotes the number of phenyl rings) were comprehensively investigated. The phosphorescence peak shifted to the shorter-wavelength side with increasing ring size of the CPPs, indicating smaller triplet energy for smaller CPPs. It was found that the triplet energy of a smaller CPP is even smaller than those of poly(p-phenylene)s, indicating that small hoop-shaped conjugated macrocycles are effective in realizing low-band gap materials. By applying laser flash photolysis, the Tn-T1 absorption spectra of CPPs were obtained, from which the size-dependence of energy levels of higher triplet states were also determined. Generation of singlet oxygen by the energy transfer from a triplet-excited CPP was confirmed. The generation yield became smaller with increasing size of the CPP in accordance with the triplet yield. From these observations, the size-dependence of the deactivation pathways is explained. PMID:24914824

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Transient F-H Center Pairs Produced from Self-Trapped Excitons at the Lowest Triplet State in Alkali Chloride Crystals

    NASA Astrophysics Data System (ADS)

    Suzuki, Yoshiro; Abe, Hidetoshi; Hirai, Masamitsu

    1992-08-01

    Time delayed double excitation spectroscopy in the picosecond range has revealed transient F bands due to the F center perturbed by an H center at the next nearest site, [F-H]nnn, in RbCl, KCl and NaCl single crystals after excitation of the self-trapped exciton (STE) from the lowest triplet state to higher excited states. The F band consists of a doublet peaking at 1.99 and 2.11 eV (RbCl), at 2.25 and 2.38 eV (KCl) and at 2.70 and 2.86 eV (NaCl) with the ratio of 2:1 in height in every crystal at 108 ps after the excitation. The peak positions and relative height of the doublets are understood qualitatively by the theory for the off-center type STE. No dichroism of the doublet observed by the light polarized in the [100] or [010] direction suggests rotation of the [F-H] axis during relaxation from the electronic b1u state, but not necessarily from the hole excited πg state.

  18. An optical-optical double resonance probe of the lowest triplet state of jet-cooled thiophosgene: Rovibronic structures and electronic relaxation

    NASA Astrophysics Data System (ADS)

    Fujiwara, Takashige; Lim, Edward C.; Judge, Richard H.; Moule, David C.

    2006-03-01

    The vibrational structure, rotational structure, and electronic relaxation of the "dark" T1A23(n,π*) state of jet-cooled thiophosgene have been investigated by two-color S2←T1←S0 optical-optical double resonance (OODR) spectroscopy, which monitors the S2→S0 fluorescence generated by S2←T1 excitation. This method is capable of isolating the T1 vibrational structure into a1, b1, and b2 symmetry blocks. The fluorescence-detected vibrational structure of the Tz spin state of T1 shows that the CS stretching frequency as well as the barrier height for pyramidal deformation are significantly greater in the A23(n,π*) state than in the corresponding A21(n,π*) state. The differing vibrational parameters of the T1 thiophosgene relative to the S1 thiophosgene can be attributed to the motions of unpaired electrons that are better correlated when they are in the excited singlet state than when they are in the triplet state of same electron configuration. A set of T1 structural parameters and the information concerning the T1 spin states have been obtained from least-square fittings of the rotationally resolved T1←S0 excitation spectrum. The nearly degenerate ∣x⟩ and ∣y⟩ spin states are well removed from ∣z⟩ spin component, indicating that T1 thiophosgene is a good example of case (ab) coupling. The decay of the ∣z⟩ spin state of T1 thiophosgene, obtained from time-resolved S2←T1←S0 OODR experiment, is characteristic of strong-coupling intermediate-case decay in which an initial rapid decay is followed by recurrences and/or a long-lived quasiexponential decay.

  19. 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.

  20. Triplet photophysics of multichromophoric molecules. A study of poly(N-vinylcarbazole) and meso-2,4-dicarbazolylpentane in fluid solutions

    SciTech Connect

    Haggquist, G.W.; Burkhart, R.D.

    1995-03-27

    Delayed luminescence and transient absorption experiments have been carried out on fluid solutions of poly(N-vinylcarbazole) (PVCz) and meso-2,4-dicarbazolylpentane (DCP) in benzene, cyclohexane, and 1,1-dimethylformamide (DMF). The delayed emission spectra of dilute solutions of DCP in all the solvents are similar and consist of excimeric delayed fluorescence (EDF) with a small contribution from monomeric delayed fluorescence. For PVCz in both benzene and DMF the delayed emission consists primarily of EDF at a delay of 1 {mu}s, but this signal decays away quickly leaving the excimeric phosphorescence band at longer delay times. The transient absorption spectra for DCP depend markedly upon the solvent. In benzene and cyclohexane the absorption is due to the carbazolyl triplet state, but in DMF absorbance bands due to the triplet and to radical cations and anions are found. Transient absorption spectra were also recorded for PVCz in benzene and DMF. Again, ionic species predominate in DMF and triplet states predominate in benzene, while the triplet excimer is present in both solutions. It is concluded that a conformation suitable for triplet excimer formation can be achieved within PVCz polymeric coils but cannot be formed intramolecularly within DCP.

  1. 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.

  2. 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.

  3. 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.

  4. Determination of the singlet-triplet energy separation for C{sub 60}{sup 2+} in DMSO by electron paramagnetic resonance

    SciTech Connect

    Trulove, P.C.; Carlin, R.T.; Eaton, G.R.; Eaton, S.S.

    1995-06-14

    In situ near-IR (NIR) spectra for C{sub 60}{sup 2-} generated electrochemically in DMSO (dimethyl sulfoxide) indicate 87 {+-} 10% conversion to C{sub 60}{sup 2-}. In the EPR spectra at 106 K a single line with 2-G peak-to-peak linewidth is superimposed on signals with splittings of 11 and 30 G, which is similar to spectra reported in the literature. The low intensity of the sharp EPR signals is inconsistent with assignment to the ground state of C{sub 60}{sup 2-} or to an excited state with ground-excited state separation less than kT between 4.5 and 200 K. A broad signal that has not been reported previously and increased in intensity with increasing temperature above 135 K is assigned to an excited triplet state with a singlet-triplet splitting of 600 {+-} 100 cm{sup -1}. The absolute intensity of the signal is consistent with the proposed singlet-triplet splitting. The 30-G line width of this signal corresponds to a lifetime of 2 ns, which is tentatively assigned as the lifetime of the triplet excited state. 48 refs., 7 figs.

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

    PubMed

    Bower, Jonathan P; Anastasio, Cort

    2014-04-01

    Singlet molecular oxygen (¹O₂*) can be a significant sink for a variety of electron-rich pollutants in surface waters and atmospheric drops. We recently found that ¹O₂* concentrations are enhanced by up to a factor of 10(4) on illuminated ice compared to in the equivalent liquid solution, suggesting that ¹O₂* could be an important oxidant for pollutants in snow. To examine this, here we study the degradation of three model organic pollutants: furfuryl alcohol (to represent furans), tryptophan (for aromatic amino acids), and bisphenol A (for phenols). Each compound was studied in illuminated aqueous solution and ice containing Rose Bengal (RB, a sensitizer for ¹O₂*) and sodium chloride (to adjust the concentration of total solutes). The RB-mediated loss of each organic compound is enhanced on illuminated ice compared to in solution, by factors of 6400 for furfuryl alcohol, 8300 for tryptophan, and 50 for bisphenol A for ice containing 0.065 mM total solutes. Rates of loss of furfuryl alcohol and tryptophan decrease at a higher total solute concentration, in qualitative agreement with predictions from freezing-point depression. In contrast, the loss of bisphenol A on ice is independent of total solute concentration. Relative to liquid tests, the enhanced loss of tryptophan on ice during control experiments made with deoxygenated solutions and solutions in D₂O show that the triplet excited state of Rose Bengal may also contribute to loss of pollutants on ice. PMID:24487942

  6. 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.

  7. Oxygen uptake induced by electron transfer from donors to the triplet state of methylene blue and xanthene dyes in air-saturated aqueous solution.

    PubMed

    Görner, Helmut

    2008-03-01

    The effects of oxygen in the photolysis of rose bengal, eosin, erythrosin and methylene blue were studied in the presence of formate and electron donors, such as ascorbic acid, aromatic amino acids or aliphatic amines, e.g. triethylamine (TEA). The overall reaction is conversion of oxygen via the hydroperoxyl/superoxide ion radical into hydrogen peroxide. The quantum yield of oxygen uptake (Phi(-O2)) increases with the donor concentration. The photoinduced formation of H2O2 is initiated by quenching of the triplet state of the dye by the donor and subsequent reactions of both the dye and donor radicals with oxygen. For methylene blue and the xanthene dyes in the presence of 10 mM ascorbic acid or 0.1 M TEA Phi(-O2)=0.07-0.25. The spectral and kinetic properties of the specific dye transients, including the radicals involved and the pH and concentration dependences, are discussed. PMID:18389155

  8. 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

  9. 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.

  10. Spin-lattice relaxation and ODMR linenarrowing of the photoexcited triplet state of pyrene in polycrystalline Shpol'skii hosts and glassy matrices

    NASA Astrophysics Data System (ADS)

    Tringali, Arthur E.; Brenner, Henry C.

    1998-01-01

    Phosphorescence and ODMR linewidths, and spin-lattice relaxation (SLR) rates were measured at pumped helium temperatures for the triplet excited state of pyrene doped in several n-alkane polycrystalline hosts as well as in 3-methylpentane (3-MP) glass, in order to test the expectation that the optimum Shpol'skii matrix for pyrene should lead to the slowest SLR rates. Among the series of n-alkanes, n-hexane showed the best Shpol'skii effect for pyrene in terms of the narrowest phosphorescence and weakest guest-host phonon coupling. The 2| E| and | D+ E| ODMR linewidths for pyrene were minimized in n-hexane as well. Microwave saturated phosphorescence decay and fast passage methods were used to measure the SLR rates in the range 1.75-4.2 K. SLR appeared to be slowest in n-octane rather than n-hexane, but was significantly faster in n-decane and 3-MP. A marked anisotropy was observed in all hosts, in which the in-plane ( x ⇄  y) relaxation rate was 20-40 times the other rates. While this was suggestive of a mechanism in which SLR occurs by means of thermal promotion to a local phonon state with rotated spin axes, the observed activation energy was too small (2-3 cm -1) to be consistent with such a mechanism. In n-hexane, the relaxation appears to proceed by means of a direct process (rate αT1) in this temperature range. In the 3-MP glass, relaxation was faster than in the polycrystalline hosts, and followed a power law temperature dependence with an exponent of 2.4±0.2, in agreement with earlier studies of naphthalene derivatives in the same host, indicating that a direct two-level-system phonon mechanism is important in this glassy host.

  11. 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.

  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.

    2014-12-23

    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

  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.

    2014-08-19

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

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

    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. 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.

  16. 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.

  17. Electronic states and spectra of BiTe

    NASA Astrophysics Data System (ADS)

    Setzer, K. D.; Laufs, S.; Fink, E. H.

    2010-09-01

    NIR/VIS emission spectra of the bismuth telluride radical, BiTe, were measured in the 3600-20 000 cm -1 region with a Fourier-transform spectrometer. BiTe was produced by reaction of bismuth and tellurium vapors and excited by energy transfer from metastable oxygen O 2( a1Δ g) in a fast-flow system. The spectrum of BiTe was found to be markedly different from those of the previously studied BiO, BiS and BiSe radicals. The A24Π 1/2 → X12Π 1/2 transition which forms the most prominent and extended band system in these molecules was not observed for BiTe, and the X22Π 3/2 → X12Π 1/2 fine structure transition shows up with a different structure and at much lower wavenumbers than in the spectra of the lighter bismuth chalcogenides. The only common feature is the C14Σ -1/2 → X12Π 1/2 system which is found in the range 16 500-19 000 cm -1 similar to the three other molecules. Besides the X2 → X1 and C1 → X1 systems, seven other transitions show up by short Δ ν = 0 sequences only. With help of the data derived from the analyses of the X2 → X1 and C1 → X1 systems and theoretical predictions of electronic and vibrational energies and transition probabilities of the strongest transitions of BiTe by Lingott et al. [7] the spectra were assigned to the transitions C14Σ -1/2 → X22Π 3/2, C14Σ -1/2 → A24Π 1/2, A44Π 1/2 → A24Π 1/2, A44Π 1/2 → X22Π 3/2, B12Π 1/2 → A24Π 1/2, B12Π 1/2 → A14Π 3/2, and B22Π 3/2 → X22Π 3/2.

  18. Ground-state features in the THz spectra of molecular clusters of β-HMX.

    PubMed

    Huang, Lulu; Shabaev, Andrew; Lambrakos, Samuel G; Massa, Lou

    2012-10-01

    We present calculations of absorption spectra arising from molecular vibrations at THz frequencies for molecular clusters of the explosive HMX using density functional theory (DFT). The features of these spectra can be shown to follow from the coupling of vibrational modes. In particular, the coupling among ground-state vibrational modes provides a reasonable molecular-level interpretation of spectral features associated with the vibrational modes of molecular clusters. THz excitation from the ground state is associated with frequencies that characteristically perturb molecular electronic states, in contrast to frequencies, which are usually substantially above the mid-infrared (mid-IR) range, that can induce appreciable electronic-state transition. Owing to this characteristic of THz excitation, one is able to make a direct association between local oscillations about ground-state minima of molecules, either isolated or comprising a cluster, and THz absorption spectra. The DFT software program GAUSSIAN was used for the calculations of the absorption spectra presented here.

  19. 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.

  20. 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.

  1. 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.

  2. Identification of Fe 3d empty states from the total current spectra of an ?(0001) surface

    NASA Astrophysics Data System (ADS)

    Møller, P. J.; Komolov, S. A.; Lazneva, E. F.

    1996-09-01

    An intensive triplet line is revealed in the total current spectrum (TCS) of a reconstructed 0953-8984/8/36/009/img7 surface. The nature of the observed structure in the TCS is discussed in comparison with previously reported data from photoemission, inverse photoemission and theoretical investigations. It is found to be a consequence of the electron transitions into an Fe 3d band of empty states. Energy locations of Fe 3d-band extrema (0953-8984/8/36/009/img8 and 0953-8984/8/36/009/img9 above the bottom of the conduction band) and its splitting 0953-8984/8/36/009/img10 are estimated from the proposed schemes of electron transitions.

  3. Electronic States and Spectra of BiO

    NASA Astrophysics Data System (ADS)

    Shestakov, O.; Breidohr, R.; Demes, H.; Setzer, K. D.; Fink, E. H.

    1998-07-01

    The electronic spectrum of the BiO radical has been studied by Fourier transform emission spectroscopy, laser-induced fluorescence, and excimer laser photolysis techniques. Six new electronic states,A1(Ω = 3/2) (Te= 11 528.8 cm-1, ωe= 530.4 cm-1, ωexe= 2.42 cm-1),G(Ω = 3/2) (Te= 20 273 cm-1, ωe= 499 cm-1, ωexe= 2.6 cm-1),H(Ω = 1/2) (Te= 20 469.76(6) cm-1, ωe= 471.63(18) cm-1, ωexe= 2.153(35) cm-1),I(Ω = 1/2) (Te= 21 982.50(2) cm-1, ωe= 506.50(11) cm-1, ωexe= 3.263(34) cm-1),J(Ω = 3/2) (Te= 25 598.95(42) cm-1, ωe= 489.95(16) cm-1, ωexe= 2.309(45) cm-1), andK(Ω = 1/2) (Te= 26 744.7(2) cm-1, ωe= 420.6(4) cm-1, ωexe= 5.25(5) cm-1), and 14 new electronic transitions (A1← X1,G → X2,H ↔ X1,H → A2(A),I ↔ X1,I → A2,J ↔ X1,J ↔ X2,K ↔ X1,K ↔ X2,K → A2,B ↔ X2,B → A2,C ↔ X2) have been detected. Time-resolved measurements of the fluorescence decays have yielded the radiative lifetimes of thev= 0 levels of most states up to <30 500 cm-1energy (τX2= 480 ± 100 μs, τA2= 9.3 ± 1.5 μs, τH= 15 ± 3 μs, τI= 16 ± 3 μs, τJ= 4.9 ± 0.9 μs, τK= 2.6 ± 0.3 μs, τB= 0.55 ± 0.08 μs, τC= 0.84 ± 0.15 μs) and rate constants for quenching of the states by some rare gas atoms and simple molecules. The new electronic statesA1,G,H,I,J, andKand the previously known levelsX1,X2,A2(A),B,C, andDare assigned to spin-orbit states arising from low-energy valence configurations of BiO with the help of detailed theoretical data calculated by Alekseyevet al.(J. Chem. Phys.100,8956-8968 (1994)).

  4. 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

  5. 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.

  6. 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.

  7. Mechanism and dynamics of intramolecular triplet state decay of 1-propyl-4-thiouracil and its α-methyl-substituted derivatives studied in perfluoro-1,3-dimethylcyclohexane.

    PubMed

    Wenska, Grazyna; Taras-Goślińska, Katarzyna; Łukaszewicz, Adam; Burdziński, Gotard; Koput, Jacek; Maciejewski, Andrzej

    2011-08-01

    The absorption, phosphorescence and phosphorescence excitation spectra, phosphorescence quantum yields, and T(1) excited state lifetimes of four 4-thiouracil derivatives were measured for the first time in chemically inert and very weakly interacting perfluoro-1,3-dimethylcyclohexane at room temperature. The set of the 4-thiouracil derivatives comprises 1-propyl-4-thiouracil (PTU) and the related compounds having a methyl substituent at the position α to the thiocarbonyl group, namely 1-propyl-4-thiothymine (PTT), 1,3-dimethyl-4-thiouracil (DMTU), and 1-methyl-3-trideuteriomethyl-4-thiouracil ([D(3)]DMTU). Quantitative information on the intramolecular decay of the T(1) excited state of the four 4-thiouracil derivatives is presented, and the mechanism and dynamics of this process are discussed. In the absence of self quenching and solvent induced deactivation, the T(1) decay of the four 4-thiouracil derivatives was dominated by intramolecular nonradiative processes (NR). The values of the rate constant k(NR) in DMTU and [D(3)]DMTU are about 4 times larger than that in PTT and about 3 times larger than that in PTU. The reasons for the enhanced nonradiative rate constant in DMTU are discussed. It is concluded that the faster rate of the nonradiative processes in DMTU is related to a larger contribution from mixing of the T(2) (nπ*) state into the lowest energy T(1) (ππ*) state, as compared to the analogous coupling in PTU and PTT. This conclusion is supported by ab initio calculations performed at the EOM-CC2/aug-cc-pVDZ level of theory. The energy spacing between the T(2) (nπ*) and T(1) (ππ*) states is estimated to be about 500, 1100, and 2000 cm(-1) for DMTU, PTU, and PTT, respectively. Among the three compounds in question, the predicted energy spacing is thus the smallest for DMTU.

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

    SciTech Connect

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

    1989-03-01

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

  9. Matrix Isolation Spectroscopy and Photochemistry of Triplet 1,3-DIMETHYLPROPYNYLIDENE (MeC3Me)

    NASA Astrophysics Data System (ADS)

    Knezz, Stephanie N.; Waltz, Terese A.; Haenni, Benjamin C.; Burrmann, Nicola J.; McMahon, Robert J.

    2015-06-01

    Acetylenic carbenes and conjugated carbon chain molecules of the HCnH family are relevant to the study of combustion and chemistry in the interstellar medium (ISM). Propynylidene (HC3H) has been thoroughly studied and its structure and photochemistry determined. Here, we produce triplet diradical 1,3-dimethylpropynylidene (MeC3Me) photochemically from a precursor diazo compound in a cryogenic matrix (N2 or Ar) at 10 K, and spectroscopic analysis is carried out. The infrared, electronic absorption, and electron paramagnetic resonance spectra were examined in light of the parent (HC3H) system to ascertain the effect of alkyl substituents on delocalized carbon chains of this type. Computational analysis, EPR, and infrared analysis indicate a triplet ground state with a quasilinear structure. Infrared experiments reveal photochemical reaction to penten-3-yne upon UV irradiation. Further experimental and computational results pertaining to the structure and photochemistry will be presented. Seburg, R. A.; Patterson, E. V.; McMahon, R. J., Structure of Triplet Propynylidene (HCCCH) as Probed by IR, UV/vis, and EPR Spectroscopy of Isotopomers. Journal of the American Chemical Society 2009, 131 (26), 9442-9455.

  10. Venus - Stein Triplet Crater

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The Magellan synthetic aperture radar (SAR) imaged this unique 'triplet crater,' or 'crater field' during orbits 418-421 on 21 September 1990. These craters are 14 kilometers, 11 kilometers, and 9 kilometers in diameter, respectively, and are centered at latitude -30.1 degrees south and longitude 345.5 degrees east. The Magellan Science Team has proposed the name Stein for this crater field after the American author, Gertrude Stein. This name has not yet been approved by the International Astronomical Union. The crater field was formed on highly fractured plains. The impacts generated a considerable amount of low viscosity 'flows' thought to consist largely of shock-melted target material along with fragmented debris from the crater. The three craters appear to have relatively steep walls based on the distortion in the image of the near and far walls of the craters in the Magellan radar look direction (from the left). The flow deposits from the three craters extend dominantly to the northeast (upper right).

  11. 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

  12. Retinopathy of Prematurity in Triplets

    PubMed Central

    Şekeroğlu, Mehmet Ali; Hekimoğlu, Emre; Çelik, Ülker; Kale, Yusuf; Baş, Ahmet Yağmur

    2016-01-01

    Objectives: To investigate the incidence, severity and risk factors of retinopathy of prematurity (ROP) in triplets. Materials and Methods: The medical records of consecutive premature triplets who had been screened for ROP in a single maternity hospital were analyzed and presence and severity of ROP; birth weight, gender, gestational age of the infant; route of delivery and the mode of conception were recorded. Results: A total of 54 triplets (40 males, 14 females) who were screened for ROP between March 2010 and February 2013 were recruited for the study. All triplets were delivered by Caesarean section and 36 (66.7%) were born following an assisted conception. During follow-up, seven (13%) of the infants developed ROP of any stage and two (3.7%) required laser photocoagulation. The mean gestational age of triplets with ROP was 27.6±1.5 (27-31) weeks whereas it was 32.0±1.5 (30-34) weeks in those without ROP (p=0.002). The mean birth weights of triplets with and without ROP were 1290.0±295.2 (970-1600) g and 1667.5±222.2 (1130-1960) g, respectively (p<0.001). The presence of ROP was not associated with gender (p=0.358) or mode of conception (p=0.674). Conclusion: ROP in triplets seems to be mainly related to low gestational age and low birth weight. Further prospective randomized studies are necessary to demonstrate risk factors of ROP in triplets and to determine if and how gemelarity plays a role in the development of ROP. PMID:27800273

  13. 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.

  14. Anomalies in vibrational spectra of hydrides of the VA group elements in the condensed state

    NASA Astrophysics Data System (ADS)

    Nabiev, Shavkat S.; Sennikov, Petr G.

    2000-12-01

    The results of a study of vibrational spectra of volatile hydrides of the VA group elements of periods 2 - 4 in the liquid state and in solutions of liquefied noble gases have been generalized and analyzed over wide frequency and temperature ranges. A number of anomalies have been revealed in the spectra of these hydrides that manifest themselves through an unusual behavior of band intensities of basic, composite vibrations and overtones on a transition from the gas phase to the condensed state, and dependences of spectroscopic and dynamic parameters as well as a non- coincidence of the line maxima in isotropic and anisotropic Raman spectra ((delta) v equals vaniso-viso) on the temperature of liquid hydrides. Mechanisms of intermolecular interactions in these liquids are discussed with the use of the as-obtained data on the intensity, frequency and shape of vibrational band contours.

  15. The electronic spectrum of Si3 I: Triplet D3h system

    NASA Astrophysics Data System (ADS)

    Reilly, N. J.; Kokkin, D. L.; Zhuang, X.; Gupta, V.; Nagarajan, R.; Fortenberry, R. C.; Maier, J. P.; Steimle, T. C.; Stanton, J. F.; McCarthy, M. C.

    2012-05-01

    We report the measurement of a jet-cooled electronic spectrum of the silicon trimer. Si3 was produced in a pulsed discharge of silane in argon, and the excitation spectrum examined in the 18 000-20 800 cm-1 region. A combination of resonant two-color two-photon ionization (R2C2PI) time-of-flight mass spectroscopy, laser-induced fluorescence/dispersed fluorescence, and equation-of-motion coupled-cluster calculations have been used to establish that the observed spectrum is dominated by the 1sideset{3}{1^' ' }}{A} - tilde{a} sideset{3}{2^' }}{A} transition of the D3h isomer. The spectrum has an origin transition at 18 600± 4 cm-1 and a short progression in the symmetric stretch with a frequency of ˜445 cm-1, in good agreement with a predicted vertical transition energy of 2.34 eV for excitation to the 1sideset{3}{1^' ' }}{A} state, which has a calculated symmetric stretching frequency of 480 cm-1. In addition, a ˜505 cm-1 ground state vibrational frequency determined from sequence bands and dispersed fluorescence is in agreement with an earlier zero-electron kinetic energy study of the lowest D3h state and with theory. A weaker, overlapping band system with a ˜360 cm-1 progression, observed in the same mass channel (m/z = 84) by R2C2PI but under different discharge conditions, is thought to be due to transitions from the (more complicated) singlet C2v ground state (1A1) state of Si3. Evidence of emission to this latter state in the triplet dispersed fluorescence spectra suggests extensive mixing in the excited triplet and singlet manifolds. Prospects for further spectroscopic characterization of the singlet system and direct measurement of the energy separation between the lowest singlet and triplet states are discussed.

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

    SciTech Connect

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

    2014-04-15

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

  19. 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

  20. Even-parity spin-triplet paired states by combined effect of Hund's rule and correlations in two-band Hubbard model: a brief overview

    NASA Astrophysics Data System (ADS)

    Zegrodnik, Michał

    2015-02-01

    Universal aspects of the Hund's rule induced spin-triplet pairing are analysed within the two-band Hubbard model on a square lattice. According to our calculations, this pairing mechanism in conjunction with the correlation effect can result in stability of the paired phase in the so-called purely repulsive interactions regime, in which there is no effectively attractive interaction. Furthermore, even though all of the interaction terms are of intrasite character, the pairing contains both intra- and inter-site components. In effect, the gap parameter has a mixture of s-wave and extended s-wave symmetries. The calculations have been carried out with the use of the Statistically Consistent Gutzwiller Approximation developed by us in recent years.

  1. Studies of low-lying triplet states in 1,3-C4F6, c-C4F6 and 2-C4F6 by electron energy-loss spectroscopy and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Limão-Vieira, P.; Duflot, D.; Anzai, K.; Kato, H.; Hoshino, M.; Silva, F. Ferreira da; Mogi, D.; Tanioka, T.; Tanaka, H.

    2013-06-01

    This Letter reports on the first measurements of the lowest lying triplet states as studied by electron energy loss spectroscopy for C4F6 isomers, hexafluoro-1,3-butadiene (1,3-C4F6), hexafluorocyclobutene (c-C4F6) and hexafluoro-2-butyne (2-C4F6). This study has been performed at an incident electron energy of 30 eV, 30°, whilst sweeping the energy loss over the range 2.0-15.0 eV. The electronic state spectroscopy has been investigated and the assignments supported by multi-reference quantum chemical calculations. The transition to the steepest electronic excited potential energy curve, is suggested to be dominant for 2-C4F6, due to the large broadening in its energy profile.

  2. 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

  3. Photoassociation and photoinduced charge transfer in bridged diaryl compounds. 6. Intramolecular triplet excimers of dicarbazolylalkanes and their comparison to an intermolecular triplet excimer of carbazole

    SciTech Connect

    Cai, J.; Lim, E.C. )

    1994-03-10

    A time-resolved emission study of intramolecular triplet excimer formation has been carried out for dicarbazolylmethane (DCM) and dicarbazolylpropane (DCP) in fluid solution at room temperature. The triplet excimer formation was deduced from the comparison of the phosphorescence with the corresponding emission from the intermolecular triplet excimer of carbazole. It has been found that whereas the triplet excimer formation in DCP is evident in both polar and nonpolar solvents, the excimer formation in DCM is observed only in polar solvents at longer delay times. The result indicates that the conformation favored by the triplet excimer is more readily attainable in DCP than in DCM. The enhancement of the triplet excimer formation by polar solvent, which is also observed for carbazole, suggests that the triplet excimers are stabilized (at least in part) by charge resonance interactions. Comparison of the temporal characteristics of the normal delayed fluorescence of DCP with those of the corresponding excimer phosphorescence suggests that the delayed fluorescence at long delay times is produced by bimolecular annihilation of the intramolecular triplet excimers. This in turn implies that the excited singlet-state species produced by bimolecular annihilation of the triplet excimers is unstable and rearranges into monomeric (i.e., non-interacting) conformation prior to its decay by emission of radiation. 16 refs., 7 figs.

  4. [C70] fullerene-sensitized triplet-triplet annihilation upconversion.

    PubMed

    Moor, Kyle; Kim, Jae-Hyuk; Snow, Samuel; Kim, Jae-Hong

    2013-11-28

    We herein report the first instance of using pristine C70 as a heavy-atom free organic sensitizer for efficient triplet-triplet annihilation upconversion (UC) for both green-to-blue and red-to-green UC using 9,10-bis(phenylethynyl)anthracene and perylene as acceptors, respectively. C70 achieved quantum yields of 8% and 0.8% for green-to-blue and red-to-green UC, 25 to 35 times higher than C60, and showed improved stability under continuous laser irradiation compared to the benchmark platinum(II)-octaethylporphyrin.

  5. Transient absorption probe of intermolecular triplet excimer of naphthalene in fluid solutions: Identification of the species based on comparison to the intramolecular triplet excimers of covalently-linked dimers

    SciTech Connect

    Wang, X.; Kofron, W.G.; Kong, S.; Rajesh, C.S.; Modarelli, D.A.; Lim, E.C.

    2000-02-24

    The authors report here the observation of the laser-induced transient absorption spectrum of intermolecular triplet excimers of naphthalene in fluid solution. This assignment is confirmed by comparison to the transient absorption spectra of the intramolecular triplet excimers of covalently linked dimers of naphthalene and quinoxaline.

  6. 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.

  7. Predicting the spin state of paramagnetic iron complexes by DFT calculation of proton NMR spectra.

    PubMed

    Borgogno, Andrea; Rastrelli, Federico; Bagno, Alessandro

    2014-07-01

    Many transition-metal complexes easily change their spin state S in response to external perturbations (spin crossover). Determining such states and their dynamics can play a central role in the understanding of useful properties such as molecular magnetism or catalytic behavior, but is often far from straightforward. In this work we demonstrate that, at a moderate computational cost, density functional calculations can predict the correct ground spin state of Fe(ii) and Fe(iii) complexes and can then be used to determine the (1)H NMR spectra of all spin states. Since the spectral features are remarkably different according to the spin state, calculated (1)H NMR resonances can be used to infer the correct spin state, along with supporting the structure elucidation of numerous paramagnetic complexes.

  8. '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.

  9. 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.

  10. 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

  11. 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

    2016-02-18

    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.

  12. 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

  13. 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

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

    PubMed

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

    2015-05-21

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

  15. Solid-state NMR spectra of lipid-anchored proteins under magic angle spinning.

    PubMed

    Nomura, Kaoru; Harada, Erisa; Sugase, Kenji; Shimamoto, Keiko

    2014-03-01

    Solid-state NMR is a promising tool for elucidating membrane-related biological phenomena. We achieved the measurement of high-resolution solid-state NMR spectra for a lipid-anchored protein embedded in lipid bilayers under magic angle spinning (MAS). To date, solid-state NMR measurements of lipid-anchored proteins have not been accomplished due to the difficulty in supplying sufficient amount of stable isotope labeled samples in the overexpression of lipid-anchored proteins requiring complex posttranslational modification. We designed a pseudo lipid-anchored protein in which the protein component was expressed in E. coli and attached to a chemically synthesized lipid-anchor mimic. Using two types of membranes, liposomes and bicelles, we demonstrated different types of insertion procedures for lipid-anchored protein into membranes. In the liposome sample, we were able to observe the cross-polarization and the (13)C-(13)C chemical shift correlation spectra under MAS, indicating that the liposome sample can be used to analyze molecular interactions using dipolar-based NMR experiments. In contrast, the bicelle sample showed sufficient quality of spectra through scalar-based experiments. The relaxation times and protein-membrane interaction were capable of being analyzed in the bicelle sample. These results demonstrated the applicability of two types of sample system to elucidate the roles of lipid-anchors in regulating diverse biological phenomena.

  16. Time and frequency resolved spectra of high molecular Rydberg states by dynamical computations

    NASA Astrophysics Data System (ADS)

    Remacle, F.; Levine, R. D.

    1997-09-01

    The absorption spectrum of bound Rydberg states which can be detected by a delayed, pulsed field ionization is computed. The spectrum, measured for various delay times, provides information on the short and the longer time dynamics of high molecular Rydberg states. A quantitative dynamical theory, based on an effective Hamiltonian formalism is applied, illustrating the role of the Rydberg electron-core coupling and of an external electrical field in the delay-time dependent spectra. The sharpening of the spectra for longer delay times is reproduced by the dynamical computations. It is found that the overall intensity, as a function of the delay time before detection, is well described by a double exponential decay where the short lifetime is primarily a manifestation of the direct autoionization to the continuum, while the long lifetime is due to interseries coupling. Both lifetimes increase with the principal quantum number of the Rydberg states. The notion of trapped "reservoir states" is illustrated by the computational results, with special reference to a kinetic model analysis. The role of the initially optically accessed state(s) and of the depth of detection, in particular with regard to the intensity, is demonstrated. The effect of varying the strength of an external dc field in the time interval prior to the detection is illustrated by the dynamical computations, with respect to both the decay kinetics and the intensity of the spectrum.

  17. 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

  18. Excited state mass spectra of doubly heavy baryons {Ω _{cc}}, {Ω _{bb}}, and {Ω _{bc}}

    NASA Astrophysics Data System (ADS)

    Shah, Zalak; Thakkar, Kaushal; Rai, Ajay Kumar

    2016-10-01

    We discuss the mass spectrum of Ω baryon with two heavy quarks and one light quark ( ccs, bbs, and bcs). The main goal of the paper is to calculate the ground state masses and after that, the positive and negative parity excited states masses are also obtained within a hypercentral constituent quark model, using Coulomb plus linear potential framework. We also added a first order correction to the potential. The mass spectra up to 5S for radial excited states and 1P-5P, 1D-4D, and 1F-2F states for orbital excited states are computed for Ω _{cc}, Ω _{bb}, and Ω _{bc} baryons. Our obtained results are compared with other theoretical predictions, which could be a useful complementary tool for the interpretation of experimentally unknown heavy baryon spectra. The Regge trajectory is constructed in both the (n_r, M2) and the ( J, M2) planes for Ω _{cc}, Ω _{bb}, and Ω _{bc} baryons and their slopes and intercepts are also determined. Magnetic moments of doubly heavy Ω 's are also calculated.

  19. Resonance-enhanced multiphoton ionization of CH₂Br₂: Rydberg states, photofragmentation, and CH spectra.

    PubMed

    Long, Jingming; Wang, Huasheng; Kvaran, Ágúst

    2014-03-13

    Mass-resolved (2 + n) resonance-enhanced multiphoton ionization (REMPI) spectra of CH2Br2 in the two-photon resonance excitation region from 71 200 to 82 300 cm(-1) were recorded and analyzed. Spectral structures allowed characterization of new molecular Rydberg states. C*((1)D2) was found to be an important intermediate in the photodissociation processes. A broad spectral feature peaking at about 80 663 cm(-1) in the C(+) spectrum and frequently seen in related studies is reinterpreted and associated with switching between three- and two-photon ionization of C*((1)D2). Analysis of band structures due to transitions from the A(2)Δ state of CH* that were seen in the CH(+) and C(+) REMPI spectra allowed characterization of three electronic states of CH, assigned as E(2)Π, D(2)Π, and F(2)Σ(+), which clarifies a long-term puzzle concerning the energetics of the CH radical. Predissociation of the E, D, and F states to form C*((1)D2) occurs. Bromine atomic lines were observed and are believed to be associated with bromine atom formation via predissociation of CH2Br2 Rydberg states.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  1. 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 ...

  2. Infrared Spectra and Density Functional Calculations for Singlet CH2═SiX2 and Triplet HC-SiX3 and XC-SiX3 Intermediates in Reactions of Laser-Ablated Silicon Atoms with Di-, Tri-, and Tetrahalomethanes.

    PubMed

    Cho, Han-Gook; Andrews, Lester

    2016-03-21

    Reactions of laser-ablated silicon atoms with di-, tri-, and tetrahalomethanes in excess argon were investigated, and the products were identified from the matrix infrared spectra, isotopic shifts, and density functional theory energy, bond length, and frequency calculations. Dihalomethanes produce planar singlet silenes (CH2═SiX2), and tri- and tetrahalomethanes form triplet halosilyl carbenes (HC-SiX3 and XC-SiX3). The Si-bearing molecules identified are the most stable, lowest-energy product in the reaction systems. While the C-Si bond in the silene is a true double bond, the C-Si bond in the carbene is a shortened single bond enhanced by hyperconjugation of the two unpaired electrons on C to σ*(Si-X) orbitals, which contributes stabilization through a small amount of π-bonding and reduction of the HCSi or XCSi angles. The C-Si bond lengths in these carbenes (1.782 Å for HC-SiF3) are between the single-bond length in the unobserved first insertion intermediate (1.975 Å for CHF2-SiF) and the double-bond length in the silene (1.704 Å for CHF═SiF2). The silicon s(2)p(2) and titanium s(2)d(2) electron configurations produce similar primary products, but the methylidyne with Ti has a bond to carbon stronger than that of the halosilyl carbene.

  3. 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.

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

    DOE PAGESBeta

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

    2016-03-01

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

  5. Tetrahydrobenzenes: Singlet-triplet separations and vibrational frequencies

    SciTech Connect

    Bettinger, H.F.; Schleyer, P.V.R.; Schaefer, H.F. III

    1999-03-31

    The energies and structures of the three tetradehydrobenzene (C{sub 6}H{sub 2}) isomers (ortho, meta, and para) were studied employing density functional theory (BLYP and B3LYP), complete active space SCF (CASSCF), and the coupled-cluster method with single, double (CCSD), and perturbative triple excitations [CCSD(T)] in conjunction with basis sets of up to triple-{zeta} plus double polarization quality. The meta isomer, 1,2,3,5-tetradehydrobenzene, is the most favorable cyclic isomer, but is 38 kcal mol{sup {minus}1} less stable than the hexatriyne C{sub 6}H{sub 2} global minimum. All of the cyclic isomers have singlet ground states, but these are less stable for the ortho and para isomers; hence, the singlet-triplet energy splittings for 1,2,4,5- and 1,2,3,4-tetradehydrobenzene are smaller than for ortho-benzyne. Harmonic vibrational frequency analyses [up to CCSD(T)/TZ2P] suggest that the {nu}{sub as}(C{triple{underscore}bond}C) vibration should be observable in the IR spectra of 1,2,4,5-tetradehydrobenzene at ca. 1,675 cm{sup {minus}1} but that this vibration might be too weak to be seen for 1,4-bis(trifluoromethyl)-2,3,5,6-tetradehydrobenzene.

  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. Electron number dependence of spin triplet-singlet relaxation time

    NASA Astrophysics Data System (ADS)

    Li, H. O.; Xiao, M.; Cao, G.; You, J.; Guo, G. P.

    2014-02-01

    In a GaAs single quantum dot, the relaxation time T1 between spin triplet and singlet states has been measured for the last few even electron numbers. The singlet-triplet energy separation EST is tuned as a control parameter for the comparison of T1 between different electron numbers. T1 steadily decreases with increasing electron numbers from 2-electrons to 6-electrons. This implies an enhancement of the spin-orbit coupling strength due to multi-electron interaction in a quantum dot.

  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. 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.

  10. Diffusion length and Langevin recombination of singlet and triplet excitons in organic heterojunction solar cells.

    PubMed

    Ompong, David; Singh, Jai

    2015-04-27

    We derived new expressions for the diffusion length of singlet and triplet excitons by using the Föster and Dexter transfer mechanisms, respectively, and have found that the diffusion lengths of singlet and triplet excitons are comparable. By using the Langevin recombination theory, we derived the rate of recombination of dissociated free charges into their excitonic states. We found that in some organic polymers the probabilities of recombination of free charge carriers back into the singlet and triplet states are approximately 65.6 and 34.4 %, respectively, indicating that Langevin-type recombination into triplet excitons in organic semiconductors is less likely. This implies that the creation of triplet excitons may be advantageous in organic solar cells, because this may lead to dissociated free charge carriers that can be collected at their respective electrodes, which should result in better conversion efficiency.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Rapid assignment of solution 31P NMR spectra of large proteins by solid-state spectroscopy.

    PubMed

    Iuga, Adriana; Spoerner, Michael; Ader, Christian; Brunner, Eike; Kalbitzer, Hans Robert

    2006-07-21

    The application of the (31)P NMR spectroscopy to large proteins or protein complexes in solution is hampered by a relatively low intrinsic sensitivity coupled with large line widths. Therefore, the assignment of the phosphorus signals by two-dimensional NMR methods in solution is often extremely time consuming. In contrast, the quality of solid-state NMR spectra is not dependent on the molecular mass and the solubility of the protein. For the complex of Ras with the GTP-analogue GppCH(2)p we show solid-state (31)P NMR methods to be more sensitive by almost one order of magnitude than liquid-state NMR. Thus, solid-state NMR seems to be the method of choice for obtaining the resonance assignment of the phosphorus signals of protein complexes in solution. Experiments on Ras.GDP complexes show that the microcrystalline sample can be substituted by a precipitate of the sample and that unexpectedly the two structural states observed earlier in solution are present in crystals as well.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

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

    PubMed

    Jávorfi, T; Garab, G; Naqvi, K R

    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 Chla/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 (Chla) 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 Chla 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 Chla/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 Tm

  4. Conformational states of N-acylalanine dithio esters: correlation of resonance Raman spectra with structures

    SciTech Connect

    Lee, H.; Angus, R.H.; Storer, A.C.; Varughese, K.I.; Carey, P.R.

    1988-01-12

    The conformational states of N-acylalanine dithio esters, involving rotational isomers about the RC(=O)NH-CH(CH/sub 3/) and NHCH(CH/sub 3/)-C(=S) bonds, are defined and compared to those of N-acylglycine dithio esters. The structure of N-(p-nitrobenzoyl)-DL-alanine ethyl dithio ester has been determined by X-ray crystallographic analysis; it is a B-type conformer with the amide N atom cis to the thiol sulfur. Raman and resonance Raman (RR) measurements on this compound and for the B conformers of solid N-benzoyl-DL-alanine ethyl dithio ester and N-(..beta..-phenylpropionyl)-DL-alanine ethyl dithio ester and its NHCH(CD/sub 3/)C(=S) and NHCH(CH/sub 3/)/sup 13/C(=S) analogues are used to set up a library of RR data for alanine-based dithio esters in a B-conformer state. RR data for this solid material in its isotopically unsubstituted and CH(C-D/sub 3/)C(=S) and CH(CH/sub 3/)/sup 13/C(=S) forms provide information on the RR signatures of alanine dithio esters in A-like conformations. RR spectra are compared for the solid compounds, for N-(p-nitrobenzoyl)-DL-alanine, N-(..beta..-phenylpropionyl)-DL-alanine, and (methyloxycarbonyl)-L-phenylalanyl-DL-alanine ethyl dithio ester, and for several /sup 13/C=S- and CD/sub 3/-substituted analogues in CCl/sub 4/ or aqueous solutions. The RR data demonstrate that the alanine-based dithio esters take up A, B, and C/sub 5/ conformations in solution. The RR spectra of these conformers are clearly distinguishable from those for the same conformers of N-acylglycine dithio esters. However, the crystallographic and spectroscopic results show that the results show that the conformational properties of N-acylglycine and N-acylalanine dithio esters are very similar.

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

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

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

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

    SciTech Connect

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

    2013-12-07

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

  7. 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.

  8. Charge Prediction Machine: A tool for inferring precursor charge states of Electron Transfer Dissociation tandem mass spectra

    PubMed Central

    Carvalho, Paulo C; Cociorva, Daniel; Wong, Catherine; Carvalho, Maria da Gloria da C; Barbosa, Valmir C; Yates, John R

    2010-01-01

    Electron Transfer Dissociation (ETD) can dissociate highly charged ions. Efficient analysis of ions dissociated with ETD requires accurate determination of charge states for calculation of molecular weight. We created an algorithm to assign the charge state of ions often used for ETD. The program, Charge Prediction Machine (CPM), uses Bayesian decision theory to account for different charge reduction processes encountered in ETD, and can also handle multiplex spectra. CPM correctly assigned charge states to 98% of the 13,097 MS2 spectra from a combined dataset of four experiments. In a comparison between CPM and a competing program, Charger (ThermoFisher), CPM produced half the mistakes. PMID:19203245

  9. 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.

  10. 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.

  11. The near elimination of triplets in IVF.

    PubMed

    Gerris, Jan

    2007-01-01

    In Antwerp, single embryo transfers (SET) have increased, and this change in policy has seen the incidence of singletons rise from 70 to 90%, twins drop from 25 to 10%, and triplets drop from 1-2% to none at all. At a national and regional level, changes have been much more dramatic as a result of a change in the law in 2003 mandating SET. Data show a huge increase in the number of treatment cycles and a dramatic rise in SET. Rates of twins and triplets have dropped considerably. European data indicate wide differences in the incidence of triplets between countries, varying between 0% (e.g.Slovenia, Iceland, Lithuania) and 4.4% (Hungary), but almost nothing is known about the true incidence of fetal reduction. US data indicate some decrease in triplets during recent years, but certainly nowhere near elimination. These data suggest that in some countries, IVF triplets have almost been eliminated, but the problem is masked by significant fetal reductions. Where SET is not widely used, triplets are still frequent. A correlation appears to exist between the percentage of SET cycles and the incidence of triplets. It is suggested that the solution to almost totally eliminate triplets after IVF is single embryo transfer.

  12. Assignment of bacteriochlorophyll a ligation state from absorption and resonance raman spectra

    SciTech Connect

    Callahan, P.M.; Cotton, T.M.

    1987-11-11

    Absorption and Soret excitation resonance Raman (RR) spectra have been obtained for a series of coordination forms on monomeric bacteriochlorophyll a (BChl a). Strong and moderate intensity bands are observed in the RR spectrum at 1609 and 1530 cm/sup -1/ for five-coordinate species, which shift to 1595 and 1512 cm/sup -1/, respectively, in the six-coordinate form. These coordination-sensitive vibrations are independent of the nature of the axial ligand and are suggested to have significant C/sub a/ C/sub m/ character, while several other less intense coordination-sensitive bands at 1463, 1444, and 1375 cm/sup -1/ are considered to arise from C/sub b/C/sub b/ and C/sub a/N stretching vibrations. These coordination-sensitive RR bands were used to determine BChl a ligation state in the solvents used, and structure correlations based on absorption maxima have been developed. The Q/sub x/ absorption band position is sensitive not only to BChl a Mg/sup 2 +/ coordination number but also to the nature of the axial ligand, i.e., oxygen, sulfur, or nitrogen. Q/sub x/ maxima are observed at 570, 575-580, and 582 nm for five-coordinate oxygen, sulfur, and nitrogen ligands, respectively, and at 590-595 and 605-612 nm, for six-coordinate oxygen and nitrogen species, respectively. The Q/sub y/ absorption maximum is insensitive to coordination number changes but is dependent on the nature of the axial ligand: 770 nm for oxygen ligand(s) and 775 nm for nitrogen ligand(s). A similar series of absorption and Soret excitation RR spectra were obtained for the demetalated form of BChl a, BPheo a.

  13. 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.

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

    PubMed

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

    2014-01-21

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

  15. Calculation of vibrational and electronic excited state absorption spectra of arsenic-water complexes using density functional theory

    NASA Astrophysics Data System (ADS)

    Huang, L.; Lambrakos, S. G.; Shabaev, A.; Massa, L.

    2016-05-01

    Calculations are presented of vibrational and electronic excited-state absorption spectra for As-H2O complexes using density function theory (DFT) and time-dependent density functional theory (TD-DFT). DFT and TD-DFT can provide interpretation of absorption spectra with respect to molecular structure for excitation by electromagnetic waves at frequencies within the IR and UV-visible ranges. The absorption spectrum corresponding to excitation states of As-H2O complexes consisting of relatively small numbers of water molecules should be associated with response features that are intermediate between that of isolated molecules and that of a bulk system. DFT and TD-DFT calculated absorption spectra represent quantitative estimates that can be correlated with additional information obtained from laboratory measurements and other types of theory based calculations. The DFT software GAUSSIAN was used for the calculations of excitation states presented here.

  16. 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.

  17. A new algorithm for predicting triplet-triplet energy-transfer activated complex coordinate in terms of accurate potential-energy surfaces

    NASA Astrophysics Data System (ADS)

    Frutos, Luis Manuel; Castaño, Obis

    2005-09-01

    The new algorithm presented here allows, for the first time, the determination of the optimal geometrical distortions that an acceptor molecule in the triplet-triplet energy-transfer process undergoes, as well as the dependence of the activation energy of the process on the triplet energy difference of donor and acceptor molecules. This algorithm makes use of the complete potential-energy surfaces (singlet and triplet states), and contrasts with the first-order approximation already published [L. M. Frutos, O. Castaño, J. L. Andrés, M. Merchán, and A. U. Acuña, J. Chem. Phys. 120, 1208 (2004)] in which an expansion of the potential-energy surfaces was used. This algorithm is gradient based and finds the best trajectory for the acceptor molecule, starting from S0 ground-state equilibrium geometry, to achieve the maximum variation of the singlet-triplet energy gap with the minimum energy of activation on S0. Therefore, the algorithm allows the determination of a "reaction path" for the triplet-triplet energy-transfer processes. Also, the algorithm could also serve eventually to find minimum-energy crossing (singlet-triplet) points on the potential-energy surface, which can play an important role in the intersystem crossing process for the acceptor molecules to recover their initial capacity as acceptors. Also addressed is the misleading use of minimum-energy paths in T1 to describe the energy-transfer process by comparing these results with those obtained using the new algorithm. The implementation of the algorithm is illustrated with different potential-energy surface models and it is discussed in the frame of nonvertical behavior.

  18. 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.

  19. 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.

  20. 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

  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. 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

  3. 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

  4. Measuring oxygen pressures using triplet quenching of Pd-porphine

    NASA Astrophysics Data System (ADS)

    Sinaasappel, Michiel; Ince, C.; Sanderse, E. A.; Bruining, Hajo A.

    1994-02-01

    A non-invasive optical method for measuring free oxygen in vivo is described. The method, introduced by Wilson and co-workers, is based on the quenching of the triplet state of Pd- porphine by oxygen and is described by the Stern-Volmer relation. The quenching of the triplet state is determined by measurement of the phosphorescence decay following excitation by a pulse of light. Measuring decay times has the advantage that they are independent of the changing optical properties of tissue and concentration of the dye. We describe a setup to measure the phosphorescence decay and present the values of Kq and (tau) o as a function of pH and temperature. Furthermore, some experiments on a rat liver and gut are presented.

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

    PubMed

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

    2013-07-01

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

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

    SciTech Connect

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

    2010-06-20

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

  7. Type-III seesaw fermionic triplets at high energy e+e- collider

    NASA Astrophysics Data System (ADS)

    Goswami, Deepanjali; Poulose, Poulose

    2016-03-01

    We investigate the signature of heavy fermionic triplets belonging to Type-III seesaw model through their direct production at the high energy e+e- collider. Single and pair production of the charged (Σ+/-) and neutral (Σ0) triplets through the processes, e+e- -->Σ+Σ- ,Σ0Σ0 ,Σ0 ν ,Σ+/- l are considered for the study. The subsequent decay of the triplets to the detector level final states are studied with the corresponding Standard Model (SM) background processes. The decay distributions are considered in details to identify the significant channels, after devising and employing suitable methods to reduce backgrounds and enhance the signal significance. Advantage of single triplet production in association with the charged SM leptons to investigate the mixing of the triplet with the SM leptons is exploited. Preliminary results show the presence of charged fermionic triplets up to a mass of ~ 950 GeV could be established through the single production at 1 TeV ILC, assuming a fermionic triplet electron mixing of 0.05 and a moderate integrated luminosity of 300 fb-1 . Further, constraints in the mass-mixing are obtained for different CM energies assuming different luminosities.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Dynamics of intramolecular electron transfer reaction of FAD studied by magnetic field effects on transient absorption spectra.

    PubMed

    Murakami, Masaaki; Maeda, Kiminori; Arai, Tatsuo

    2005-07-01

    The kinetics of intermediates generated from intramolecular electron-transfer reaction by photo irradiation of the flavin adenine dinucleotide (FAD) molecule was studied by a magnetic field effect (MFE) on transient absorption (TA) spectra. Existence time of MFE and MFE action spectra have a strong dependence on the pH of solutions. The MFE action spectra have indicated the existence of interconversion between the radical pair and the cation form of the triplet excited state of flavin part. All rate constants of the triplet and the radical pair were determined by analysis of the MFE action spectra and decay kinetics of TA. The obtained values for the interconversion indicate that the formation of cation radical promotes the back electron-transfer reaction to the triplet excited state. Further, rate constants of spin relaxation and recombination have been studied by the time profiles of MFE at various pH. The drastic change of those two factors has been obtained and can be explained by SOC (spin-orbit coupling) induced back electron-transfer promoted by the formation of a stacking conformation at pH > 2.5.

  14. 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

  15. 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.

  16. Cooper pairs spintronics in triplet spin valves.

    PubMed

    Romeo, F; Citro, R

    2013-11-27

    We study a spin valve with a triplet superconductor spacer intercalated between two ferromagnets with noncollinear magnetizations. We show that the magnetoresistance of the triplet spin valve depends on the relative orientations of the d vector, characterizing the superconducting order parameter, and the magnetization directions of the ferromagnetic layers. For devices characterized by a long superconductor, the effects of a polarized current sustained by Cooper pairs only are observed. In this regime, a supermagnetoresistance effect emerges, and the chiral symmetry of the order parameter of the superconducting spacer is easily recognized. Our findings open new perspectives in designing spintronics devices based on the cooperation of ferromagnetic and triplet correlations.

  17. Cooper pairs spintronics in triplet spin valves.

    PubMed

    Romeo, F; Citro, R

    2013-11-27

    We study a spin valve with a triplet superconductor spacer intercalated between two ferromagnets with noncollinear magnetizations. We show that the magnetoresistance of the triplet spin valve depends on the relative orientations of the d vector, characterizing the superconducting order parameter, and the magnetization directions of the ferromagnetic layers. For devices characterized by a long superconductor, the effects of a polarized current sustained by Cooper pairs only are observed. In this regime, a supermagnetoresistance effect emerges, and the chiral symmetry of the order parameter of the superconducting spacer is easily recognized. Our findings open new perspectives in designing spintronics devices based on the cooperation of ferromagnetic and triplet correlations. PMID:24329463

  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. 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.

  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.

  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. 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

  4. Role of triplet polaron pairs in conjugated polymer photophysics

    NASA Astrophysics Data System (ADS)

    Wesely, Elizabeth; Rothberg, Lewis; Marchetti, Alfred; Chen, Shaw; Geng, Yanhou; Culligan, Sean

    2007-03-01

    We measure the decay of the long-lived fluorescence of a conjugated oligofluorene at temperatures from 300 K to 20 K. We conclude that nearly all of this emission arises from geminate recombination of photogenerated polaron pairs to reform the singlet exciton, and that charge pair recombination represents a significant contribution to the overall fluorescence quantum yield. The unusual nonmonotonic decay dynamics of the delayed fluorescence can be explained if we assume interconversion between singlet and triplet polaron pairs on the submicrosecond time scale. (˜500 ns.) We are able to model the decay of the delayed fluorescence by assuming activated recombination from a Gaussian energy distribution of singlet polaron pairs centered 0.2 eV below the excited state and having a standard deviation of 0.12 eV. The model is relevant to recent work involving the measurement of singlet-triplet branching ratios and to the yields of electroluminescent devices.

  5. 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.

  6. 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.

  7. 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.

  8. Atomistic modeling of two-dimensional electronic spectra and excited-state dynamics for a Light Harvesting 2 complex.

    PubMed

    van der Vegte, C P; Prajapati, J D; Kleinekathöfer, U; Knoester, J; Jansen, T L C

    2015-01-29

    The Light Harvesting 2 (LH2) complex is a vital part of the photosystem of purple bacteria. It is responsible for the absorption of light and transport of the resulting excitations to the reaction center in a highly efficient manner. A general description of the chromophores and the interaction with their local environment is crucial to understand this highly efficient energy transport. Here we include this interaction in an atomistic way using mixed quantum-classical (molecular dynamics) simulations of spectra. In particular, we present the first atomistic simulation of nonlinear optical spectra for LH2 and use it to study the energy transport within the complex. We show that the frequency distributions of the pigments strongly depend on their positions with respect to the protein scaffold and dynamics of their local environment. Furthermore, we show that although the pigments are closely packed the transition frequencies of neighboring pigments are essentially uncorrelated. We present the simulated linear absorption spectra for the LH2 complex and provide a detailed explanation of the states responsible for the observed two-band structure. Finally, we discuss the energy transfer within the complex by analyzing population transfer calculations and 2D spectra for different waiting times. We conclude that the energy transfer from the B800 ring to the B850 ring is mediated by intermediate states that are delocalized over both rings, allowing for a stepwise downhill energy transport.

  9. Absolute structural elucidation of natural products--a focus on quantum-mechanical calculations of solid-state CD spectra.

    PubMed

    Pescitelli, Gennaro; Kurtán, Tibor; Flörke, Ulrich; Krohn, Karsten

    2009-01-01

    In this review article we examine state-of-the-art techniques for the structural elucidation of organic compounds isolated from natural sources. In particular, we focus on the determination of absolute configuration (AC), perhaps the most challenging but inevitable step in the whole process, especially when newly isolated compounds are screened for biological activity. Among the many methods employed for AC assignment that we review, special attention is paid to electronic circular dichroism (CD) and to the modern tools available for quantum-mechanics CD predictions, including TDDFT. In this context, we stress that conformational flexibility often poses a limit to practical CD calculations of solution CD spectra. Many crystalline natural products suitable for X-ray analysis do not contain heavy atoms for a confidential AC assignment by resonant scattering. However, their CD spectra can be recorded in the solid state, for example with the KCl pellet technique, and analyzed possibly by nonempirical means to provide stereochemical information. In particular, solid-state CD spectra can be compared with those calculated with TDDFT or other high-level methods, using the X-ray geometry as input. The solid-state CD/TDDFT approach, described in detail, represents a quick and reliable tool for AC assignment of natural products.

  10. Triplet-triplet energy transfer in fucoxanthin-chlorophyll protein from diatom Cyclotella meneghiniana: insights into the structure of the complex.

    PubMed

    Di Valentin, Marilena; Meneghin, Elena; Orian, Laura; Polimeno, Antonino; Büchel, Claudia; Salvadori, Enrico; Kay, Christopher W M; Carbonera, Donatella

    2013-10-01

    Although the major light harvesting complexes of diatoms, called FCPs (fucoxanthin chlorophyll a/c binding proteins), are related to the cab proteins of higher plants, the structures of these light harvesting protein complexes are much less characterized. Here, a structural/functional model for the "core" of FCP, based on the sequence homology with LHCII, in which two fucoxanthins replace the central luteins and act as quenchers of the Chl a triplet states, is proposed. Combining the information obtained by time-resolved EPR spectroscopy on the triplet states populated under illumination, with quantum mechanical calculations, we discuss the chlorophyll triplet quenching in terms of the geometry of the chlorophyll-carotenoid pairs participating to the process. The results show that local structural rearrangements occur in FCP, with respect to LHCII, in the photoprotective site.

  11. 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.

  12. Pregnancy outcome of early multifetal pregnancy reduction: triplets to twins versus triplets to singletons.

    PubMed

    Haas, Jigal; Hourvitz, Ariel; Dor, Jehoshua; Yinon, Yoav; Elizur, Shai; Mazaki-Tovi, Shali; Barzilay, Eran; Shulman, Adrian

    2014-12-01

    Multifetal pregnancy reduction (MPR) of triplets to twins results in improved pregnancy outcomes compared with triplet gestations managed expectantly. Perinatal outcomes of early transvaginal MPR from triplets to twins were compared with reduction from triplets to singletons. Seventy-four trichorionic triplet pregnancies that underwent early transvaginal MPR at 6-8 weeks gestation were included. Cases were divided into two groups according to the initial procedure: reduction to twin (n = 55) or to singleton (n = 19) gestations. Infants from triplet pregnancies reduced to twins were delivered earlier (36.6 versus 37.9 weeks; P = 0.04) and had lower mean birth weights (2364 g versus 2748 g; P = 0.02) compared with those from triplets reduced to singleton gestations. The rates of pregnancy loss before 24 weeks (3.6% versus 5.3%), as well as of preterm delivery before 32 and 34 weeks of gestation (0% versus 5.3% and 7.3% versus 5.3%, respectively) were similar between the twin and singleton pregnancies. No significant difference was found in the prevalence of gestational diabetes (15.1% versus 5.6%) or gestational hypertension (24.5% versus 16.7%) between the groups. Selective reduction of triplet pregnancies to singleton rather than twin gestations is associated with improved outcomes. PMID:25444505

  13. Observations of the O I lambda 7773 triplet in intermediate-type supergiants using a linear photodiode array

    NASA Astrophysics Data System (ADS)

    Hopkinson, G. R.; Humrich, A.

    1981-05-01

    Partially resolved spectra of the infrared oxygen triplet in A-G supergiants have been obtained with a new self-scanned photodiode array system. Curve of growth analyses indicate that the lines are formed in non-LTE. A line is identified at 7777.9 A which is strong in A supergiants and which will complicate the analysis of low resolution spectra. At a resolution of 0.45 A/diode the CN lines which appear in G8 and later stars are blended with the O I triplet rendering its equivalent width unreliable as a luminosity indicator.

  14. Ab inito study on triplet excitation energy transfer in photosynthetic light-harvesting complexes.

    PubMed

    You, Zhi-Qiang; Hsu, Chao-Ping

    2011-04-28

    We have studied the triplet energy transfer (TET) for photosynthetic light-harvesting complexes, the bacterial light-harvesting complex II (LH2) of Rhodospirillum molischianum and Rhodopseudomonas acidophila, and the peridinin-chlorophyll a protein (PCP) from Amphidinium carterae. The electronic coupling factor was calculated with the recently developed fragment spin difference scheme (You and Hsu, J. Chem. Phys. 2010, 133, 074105), which is a general computational scheme that yields the overall coupling under the Hamiltonian employed. The TET rates were estimated based on the couplings obtained. For all light-harvesting complexes studied, there exist nanosecond triplet energy transfer from the chlorophylls to the carotenoids. This result supports a direct triplet quenching mechanism for the photoprotection function of carotenoids. The TET rates are similar for a broad range of carotenoid triplet state energy, which implies a general and robust TET quenching role for carotenoids in photosynthesis. This result is also consistent with the weak dependence of TET kinetics on the type or the number of π conjugation lengths in the carotenoids and their analogues reported in the literature. We have also explored the possibility of forming triplet excitons in these complexes. In B850 of LH2 or the peridinin cluster in PCP, it is unlikely to have triplet exciton since the energy differences of any two neighboring molecules are likely to be much larger than their TET couplings. Our results provide theoretical limits to the possible photophysics in the light-harvesting complexes.

  15. 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.

  16. 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.

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

    PubMed

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

    2014-09-28

    The metal L-edge (2p → 3d) X-ray absorption spectra are affected by a number of different interactions: electron-electron repulsion, spin-orbit coupling, and charge transfer between metal and ligands, which makes the simulation of spectra challenging. The core restricted active space (RAS) method is an accurate and flexible approach that can be used to calculate X-ray spectra of a wide range of medium-sized systems without any symmetry constraints. Here, the applicability of the method is tested in detail by simulating three ferric (3d(5)) model systems with well-known electronic structure, viz., atomic Fe(3+), high-spin [FeCl6](3-) with ligand donor bonding, and low-spin [Fe(CN)6](3-) that also has metal backbonding. For these systems, the performance of the core RAS method, which does not require any system-dependent parameters, is comparable to that of the commonly used semi-empirical charge-transfer multiplet model. It handles orbitally degenerate ground states, accurately describes metal-ligand interactions, and includes both single and multiple excitations. The results are sensitive to the choice of orbitals in the active space and this sensitivity can be used to assign spectral features. A method has also been developed to analyze the calculated X-ray spectra using a chemically intuitive molecular orbital picture.

  19. Spectroscopy and Photochemistry of Triplet 1,3-Dimethylpropynylidene (MeC3Me).

    PubMed

    Knezz, Stephanie N; Waltz, Terese A; Haenni, Benjamin C; Burrmann, Nicola J; McMahon, Robert J

    2016-09-28

    Photolysis (λ > 472 nm) of 2-diazo-3-pentyne (11) affords triplet 1,3-dimethylpropynylidene (MeC3Me, (3)3), which was characterized spectroscopically in cryogenic matrices. The infrared, electronic absorption, and electron paramagnetic resonance spectra of MeC3Me ((3)3) are compared with those of the parent system (HC3H) to ascertain the effect of alkyl substituents on delocalized carbon chains of this type. Quantum chemical calculations (CCSD(T)/ANO1) predict an unsymmetrical equilibrium structure for triplet MeC3Me ((3)3), but they also reveal a very shallow potential energy surface. The experimental IR spectrum of triplet MeC3Me ((3)3) is best interpreted in terms of a quasilinear, axially symmetric structure. EPR spectra yield zero-field splitting parameters that are typical for triplet carbenes with axial symmetry (|D/hc| = 0.63 cm(-1), |E/hc| = ∼ 0 cm(-1)), while theoretical analysis suggests that the methyl substituents confer significant spin polarization to the carbon chain. Upon irradiation into the near-UV electronic absorption (λmax 350 nm), MeC3Me ((3)3) undergoes 1,2-hydrogen migration to yield pent-1-en-3-yne (4), a photochemical reaction that is typical of carbenes bearing a methyl substituent. This facile process apparently precludes photoisomerization to other interesting C5H6 isomers, in contrast to the rich photochemistry of the parent C3H2 system.

  20. 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

  1. 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.

  2. 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.

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

    PubMed

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

    2014-01-21

    A definition of the triplet-triplet energy transfer reaction coordinate within the very weak electronic coupling limit is proposed, and a novel theoretical formalism is developed for its quantitative determination in terms of internal coordinates The present formalism permits (i) the separation of donor and acceptor contributions to the reaction coordinate, (ii) the identification of the intrinsic role of donor and acceptor in the triplet energy transfer process, and (iii) the quantification of the effect of every internal coordinate on the transfer process. This formalism is general and can be applied to classical as well as to nonvertical triplet energy transfer processes. The utility of the novel formalism is demonstrated here by its application to the paradigm of nonvertical triplet-triplet energy transfer involving cis-stilbene as acceptor molecule. In this way the effect of each internal molecular coordinate in promoting the transfer rate, from triplet donors in the low and high-energy limit, could be analyzed in detail. PMID:25669358

  4. 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.

  5. 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.

  6. Adsorption of acridine on silver electrode: SERS spectra potential dependence as a probe of adsorbate state

    NASA Astrophysics Data System (ADS)

    Solovyeva, Elena V.; Myund, Liubov A.; Dem'yanchuk, Evgeniya M.; Makarov, Artiom A.; Denisova, Anna S.

    2013-02-01

    This work investigates acridine adsorption on the silver electrode surface. The dependence of the acridine SERS spectra on the electrode potential proved to be quite different for azaheterocycle molecules, while the pH effect as expected. The changes in the acridine SERS spectrum caused by the double electric layer (DEL) rearrangement can be explained by sorption/desorption rather than the adsorbate molecule reorientation. The presence of chloride anions close to the silver surface is important not only for the SERS-active properties but for the formation of the stabilised surface complexes of the protonated acridine as well.

  7. 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.

  8. 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

  9. 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

  10. One Interesting Family of Diophantine Triplets

    ERIC Educational Resources Information Center

    Deshpande, M. N.

    2002-01-01

    In this note properties of two sequences generated by the recurrence relation G[subscript n] +2 = 4 G[subscript n] +1 - G[subscript n], are studied. It is shown that one of the sequences leads to a family of diophantine triplets. Some interesting properties of these sequences are also established.

  11. 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.

  12. Temperature sensitivity of molecular oxygen resonant-enhanced multiphoton ionization spectra involving the C 3Π g intermediate state

    NASA Astrophysics Data System (ADS)

    Wu, Yue; Zhang, Zhili; Adams, Steven F.

    2016-05-01

    The technique of measuring O2 rotational temperature by coherent microwave Rayleigh scattering from resonance-enhanced multiphoton ionization (Radar REMPI) has been studied to determine temperature sensitivity and range. The molecular oxygen Rydberg state of ( {3sσ } )C{{}3}Πg ( {v^' } = 2} ) has been selected as the intermediate state in the 2 + 1 REMPI process, which is known to provide a relatively strong REMPI signal. Rotational-resolved spectra representing the two-photon C{{}3}Πg ( {v^' } = 2} ) leftarrow leftarrow X{{}3}Σ g^{ - } ( {v^' ' } = 0} ) transition have been obtained under several gas conditions including pure oxygen, air-like syngas, ambient air, and flame environments from room temperature ( 300 K) to flame temperature ( 1700 K). An O2 REMPI spectral model has been developed to simulate the experimental spectral line intensity distribution which is dependent on the O2 ground-state temperature. The model has been verified at a low-temperature condition ( 5 K) and then applied to various oxygen environments over an extended temperature range with an overall error of less than ±10 %. The current O2 REMPI spectral model is an improvement over a previously reported version in both accuracy and the quantity of lines fit to provide rotational temperature measurements. This work details an optimized model that fits simulated spectra to full experimental spectral bands over various conditions with a wide temperature range, including both low temperature (<300 K) and high temperature ranges (>1300 K).

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

    NASA Astrophysics Data System (ADS)

    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.

  14. 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

  15. 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.

  16. Photochemistry of furyl- and thienyldiazomethanes: spectroscopic characterization of triplet 3-thienylcarbene.

    PubMed

    Pharr, Caroline R; Kopff, Laura A; Bennett, Brian; Reid, Scott A; McMahon, Robert J

    2012-04-11

    Photolysis (λ > 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N(2) at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm(-1), |E/hc| = 0.0554 cm(-1); |D/hc| = 0.579 cm(-1), |E/hc| = 0.0315 cm(-1)). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon-an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λ(max) = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C(5)H(4)S or C(5)H(4)O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively).

  17. 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.

  18. 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.

  19. 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.

  20. Nucleon, Delta and Omega excited state spectra at three pion mass values

    SciTech Connect

    John Bulava, Robert G. Edwards, Balint Joo, David G. Richards, Eric Engelson, Huey-Wen Lin, Colin Morningstar, Stephen J. Wallace

    2010-06-01

    The energies of the excited states of the Nucleon, Delta and Omega are computed in lattice QCD, using two light quarks and one strange quark on anisotropic lattices. The calculations are performed at three values of the pion mass: 392(4), 438(3) and 521(3) MeV. We employ the variational method with a basis of about ten interpolating operators enabling six energies to be distinguished clearly in each irreducible representation of the octahedral group. We compare our calculations of nucleon excited states with the low-lying experimental spectrum. There is reasonable agreement for the pattern of states.

  1. 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.

  2. 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

  3. H, He-like recombination spectra II: l-changing collisions for He Rydberg states

    NASA Astrophysics Data System (ADS)

    Guzmán, F.; Badnell, N. R.; Williams, R. J. R.; van Hoof, P. A. M.; Chatzikos, M.; Ferland, G. J.

    2016-09-01

    Cosmological models can be constrained by determining primordial abundances. Accurate predictions of the He I spectrum are needed to determine the primordial helium abundance to a precision of <1% in order to constrain Big Bang Nucleosynthesis models. Theoretical line emissivities at least this accurate are needed if this precision is to be achieved. In the first paper of this series, which focused on H I, we showed that differences in l-changing collisional rate coefficients predicted by three different theories can translate into 10% changes in predictions for H I spectra. Here we consider the more complicated case of He atoms, where low-l subshells are not energy degenerate. A criterion for deciding when the energy separation between l subshells is small enough to apply energy-degenerate collisional theories is given. Moreover, for certain conditions, the Bethe approximation originally proposed by Pengelly & Seaton (1964) is not sufficiently accurate. We introduce a simple modification of this theory which leads to rate coefficients which agree well with those obtained from pure quantal calculations using the approach of Vrinceanu et al. (2012). We show that the l-changing rate coefficients from the different theoretical approaches lead to differences of ˜10% in He I emissivities in simulations of H II regions using spectral code Cloudy.

  4. [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

  5. 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.

  6. 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.

  7. Singlet and triplet Bardeen-Cooper-Schrieffer pairs in a gas of two-species fermionic polar molecules

    SciTech Connect

    Shi, T.; Zhang, J.-N.; Sun, C.-P.; Yi, S.

    2010-09-15

    Taking into account the deformation of the Fermi surface, we investigate the spin-singlet and -triplet BCS pairings in a mixture of fermionic polar molecules with two different hyperfine states. In particular, we explore the relation between the critical temperatures and the Fock-exchange interaction. We also show that, by tuning short-range interaction between interspecies molecules, the singlet- and triplet-paired superfluids may coexist.

  8. 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)].

  9. Triplets in extended nematic liquid crystals and polarons in their blends

    NASA Astrophysics Data System (ADS)

    Tsoi, Wing C.; O'Neill, Mary; Aldred, Matthew P.; Vlachos, Panos; Kelly, Stephen M.

    2007-09-01

    Photoinduced absorption shows that triplets are the primary photoexcited species in a series of conjugated liquid crystals containing thiophene and fluorene groups. We find that the triplet generation rate can be varied substantially by molecular design. The introduction of extra thiophene groups into the elongated molecules changes the intersystem crossing rate by over two orders of magnitude, while modifying the singlet and triplet energies by only small amounts. This result is attributed to the high spin-orbit coupling constant of sulfur: An increase in the number of sulfur atoms increases the spin-orbit coupling between the singlet and triplet states. These results are relevant to the design of organic light emitting diodes, lasers, and other devices where triplet formation has a major impact on device performance. The molecules are shown to act as effective electron donors when blended with a perylene molecule which acts as an electron acceptor. The electron transfer rate is faster than the singlet lifetime so that the blend shows the efficient charge separation required for a photovoltaic device.

  10. Calculating the density of states and optical-absorption spectra of large quantum systems by the plane-wave moments method

    NASA Astrophysics Data System (ADS)

    Wang, Lin-Wang

    1994-04-01

    The moments method is used to calculate the density of states and optical-absorption spectra of large quantum systems. This method uses random wave functions to calculate 500 Chebyshev moments of the density of states (5002 for the optical-absorption spectra), and transforms these moments back to energy space. The results compare well with direct calculations on a large, 2048 Si-atom bulklike supercell system. To demonstrate its utility, the spectra of a realistic quantum dot with 1035 Si and 452 H atoms are calculated using an empirical pseudopotential Hamiltonian and a plane-wave basis of wave functions.

  11. 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.

  12. Disentangling entanglement spectra of fractional quantum Hall states on torus geometries.

    PubMed

    Läuchli, Andreas M; Bergholtz, Emil J; Suorsa, Juha; Haque, Masudul

    2010-04-16

    We analyze the entanglement spectrum of Laughlin states on the torus and show that it is arranged in towers, each of which is generated by modes of two spatially separated chiral edges. This structure is present for all torus circumferences, which allows for a microscopic identification of the prominent features of the spectrum by perturbing around the thin-torus limit.

  13. Excitation of {sup 1}S and {sup 3}S Metastable Helium Atoms to Doubly Excited States

    SciTech Connect

    Alagia, M.; Coreno, M.; Farrokhpour, H.; Omidyan, R.; Tabrizchi, M.; Franceschi, P.; Mihelic, A.; Zitnik, M.; Moise, A.; Prince, K. C.; Richter, R.; Soederstroem, J.; Stranges, S.

    2009-04-17

    We present spectra of triplet and singlet metastable helium atoms resonantly photoexcited to doubly excited states. The first members of three dipole-allowed {sup 1,3}P{sup o} series have been observed and their relative photoionization cross sections determined, both in the triplet (from 1s2s {sup 3}S{sup e}) and singlet (from 1s2s {sup 1}S{sup e}) manifolds. The intensity ratios are drastically different with respect to transitions from the ground state. When radiation damping is included the results for the singlets are in agreement with theory, while for triplets spin-orbit interaction must also be taken into account.

  14. 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.

  15. 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

  16. 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.

  17. Delayed interval delivery in a triplet gestation.

    PubMed

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

    2012-11-27

    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.

  18. Conductance spectra of the Fe111 compounds in the normal and superconducting states

    NASA Astrophysics Data System (ADS)

    Arham, Hamood; Park, W. K.; Greene, L. H.; Chung, D. Y.; Bugaris, D.; Kanatzidis, M. G.

    2013-03-01

    We use quasiparticle scattering spectroscopy (QPS), also known as point contact spectroscopy, to study Co doped NaFeAs. A conductance enhancement is observed in the normal state of NaFeAs with an onset temperature ~ 95 K. Our previous work on the electron and hole doped Fe122 compounds revealed that a conductance enhancement in the normal state is only observed for those compounds that have an in-plane resistive anisotropy. This enhancement is caused by the non-Fermi liquid behavior of these compounds due to orbital fluctuations. (Arham et al. PRB 85, 214515 (2012); Lee et al. arXiv:1110.5917). Our initial results indicate that the same conditions hold true for the Fe111 compounds as well. QPS is effective in detecting strong electron correlations (hybridization gap, Fano resonance, orbital fluctuations) in the normal state of a variety of strongly correlated electron systems that exhibit the ubiquitous `domed' phase diagram. The need for some kind of a microscopic theory that explains how QPS detects strong electron correlations will be discussed. This work is supported by the Center for Emergent Superconductivity, an Energy Frontier Research Center funded by the US DOE, Office of Science, Award No. DE-AC0298CH1088.

  19. Surface-state spectra from thick-oxide MOS tunnel junctions

    NASA Technical Reports Server (NTRS)

    Ma, T. P.; Barker, R. C.

    1974-01-01

    The conductance and capacitance of thick-oxide MOS tunnel junctions (SiO2 thickness 40 to 65 A) have been measured from 35 Hz to 210 kHz. It is demonstrated that the use of a thick-oxide MOS tunnel junction makes it possible to obtain the surface-state data throughout the whole silicon band gap with better resolution and better sensitivity than the conventional MOS capacitance techniques. A slight departure from equilibrium may occur in the voltage range where large tunnel current flows. Corrections to the energy scale must be made in this voltage range. A method for the evaluation of the junction quality is discussed. The simplified equivalent circuits necessary for the calculation of surface-state data are constructed under various bias conditions by an approach different from that used in a previously published work. The present work supports the model that at least some of the observed surface states are a consequence of the diffusion of contact metals into the oxide.

  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. A simple method to determine bond lengths and excited state surfaces from electronic-vibrational spectra

    NASA Astrophysics Data System (ADS)

    Lee, Soo-Y.; Lai, Choy-Heng

    1990-03-01

    A fast and efficient method using the spectral moments of an electronic—vibrational spectrum is described to determine the harmonic and Morse potential fits to the excited state potential in the Franck—Condon region. Some of the drawbacks of the Franck—Condon least-squares fitting procedure are overcome by the moment method. The method is applied to some diatomics of current interest, spanning a wide range of bond length change in the electronic transition. The accuracy of the results suggests that the spectral moment method can be a replacement for the traditional and still popular Franck—Condon analysis.

  2. Trion spectra of semiconductor nanostructures

    NASA Astrophysics Data System (ADS)

    Esser, Axel; Runge, Erich; Zimmermann, Roland

    2001-03-01

    The linear optical properties of quantum wells and quantum wires in the presence of a moderate background carrier density nB are investigated theoretically and compared with recent experiments. At low n_B, excitons and trions (charged excitons) are the relevant excitations. We present a density-matrix approach, which starts from the interband polarization and couples directly to higher order correlation functions which are related to three-particle excitations. It allows to describe both trionic and excitonic states. A generalized dynamical truncation scheme is applied and yields an expression for the absorption coefficient of trions in terms of trion eigenstates. Then, in combination with a numerical solution of the three-particle Schrödinger equation we sucessfully model (i) experimental photoluminescence lineshapes (their asymmetry towards lower photon energy and temperature-dependence is related to carrier recoil) [1], (ii) radiative trion lifetime (shown to depend linearly on temperature for a thermalized trion distribution) [2], and (iii) the influence of an electrical field (quantum-confined Stark effect) [3]. The optical response of excitons and trions can be studied alternatively by the solution of the time-dependent trion Schrödinger equation yielding information about (i) the appearance of trion triplet states (shown to be optically inactice at vanishing center-of-mass momentum), and (ii) exciton-electron scattering states (which give rise to a broadening of the high-energy side of the exciton). Altogether, a consistent and thorough picture of exciton related absorption spectra in the presence of additional carriers can be derived either from density matrix theory or the solution of the time-dependent three-particle Schrödinger equation. [1] A. Esser et al., Phys. Rev. B 62, 8232 (2000); [2] V. Ciulin et al., Phys. Rev. B (2000); [3] A. Esser et al., Phys. Status Solidi B 221, 281 (2000).

  3. 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

  4. 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.

  5. I Search of Narrow Proton-Antiproton Bound States: High Resolution Gamma and Charged Flow Pion Spectra from Protonium.

    NASA Astrophysics Data System (ADS)

    Petridou, Chariclia I.

    We studied the pp annihilations at rest looking for narrow bound states in the proton-antiproton system. We looked, with high energy resolution, for radiative and pionic transitions in the gamma and charged pion spectra. The detector for the (gamma)(--->)e+e- and the (pi)('(+OR-)) was a magnetic pair spectrometer. The directions of the incident particles (e(+OR-) and (pi)(+OR-)) were determined by a drift chamber module in front of the magnet and the final directions of the particles, if reflected in the magnet, by the same chamber; if transversing the magnet, by an identical module at the rear of the magnet. The momentum was calculated from the directions of the particle. The following gamma spectra were obtained. Gammas with both e+, e- reflected in the magnet at a field of about 6 Kgauss (RR-gammas). That covers the region between 80 and 180 MeV, corresponding to a missing mass 1794 to 1686 MeV/c. The energy resolution is about 2.5 MeV ((sigma)) at 129 MeV (confirmed by the observed Panofsky gammas from stopping (pi)('-)p data) and 5 MeV ((sigma)) at 80 MeV. We have no evidence for narrow peaks except for the Panofsky gamma produced with a branching ratio of 3.3 x 10('-3) from (pi)('-) stops in the target. Upper limits for (gamma) -transitions in the region between 80 to 180 MeV were set at about 10('-3). Gammas with one e+(e-) reflected and the other transversing the magnet (RP-gammas) for fields of about 6 and 12 Kgauss, covering the region (GREATERTHEQ) 200 MeV, which corresponds to missing mass (LESSTHEQ) 1664 MeV/c('2). The gamma energy resolution in MeV is 51(.)E('2) (GeV) and 25.5(.)E('2)(GeV) for the low and high field respectively. Finally the charged pion spectra for those transversing the magnet are given for both magnet settings and as a function of charge multiplicity, covering the momentum region from (GREATERTHEQ) 150 MeV/c. The momentum resolution is the same as that for the RP-gammas. The two body annihilations (pi)('+)(pi)('-) and (pi

  6. 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

  7. 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.}

  8. 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.

  9. 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.

  10. Simulating the peptide folding kinetic related spectra based on the Markov State Model.

    PubMed

    Song, Jian; Zhuang, Wei

    2014-01-01

    Optical spectroscopic tools are used to monitor protein folding/unfolding dynamics after a fast triggering such as the laser induced temperature jump. These techniques provide new opportunities for comparison between theory and simulations and atom-level understanding protein folding mechanism. However, the direct comparison still face two main challenges: a gap between folding relevant timescales (microseconds or above) and length of molecular dynamics simulations (typically tens to hundreds of nanoseconds), and difficulty in directly calculating spectroscopic observables from simulation configurations. Markov State Model (MSM) approach is one of the most powerful means which can increase simulations timescale up to microsecond or even millisecond. We address progress on modeling infrared and fluorescence spectroscopic signals of temperature jump induced unfolding dynamics for a few small proteins. The harmoniousness between experiment and theoretical can both improve our understanding of protein folding mechanisms and provide direct validation of those theoretical models. PMID:24446363

  11. Final State Projection Method in Charge-Transfer Multiplet Calculations: An analysis of Ti L-edge Absorption Spectra

    PubMed Central

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

    2016-01-01

    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 d0 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 non-trivial spectral assignment, which makes a detailed theoretical description of experimental spectra valuable for the analysis of bonding. PMID:26226507

  12. 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

  13. 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

  14. 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.

  15. 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

  16. Dye-Sensitized Solar Cell with Integrated Triplet-Triplet Annihilation Upconversion System.

    PubMed

    Nattestad, Andrew; Cheng, Yuen Yap; MacQueen, Rowan W; Schulze, Tim F; Thompson, Fletcher W; Mozer, Attila J; Fückel, Burkhard; Khoury, Tony; Crossley, Maxwell J; Lips, Klaus; Wallace, Gordon G; Schmidt, Timothy W

    2013-06-20

    Photon upconversion (UC) by triplet-triplet annihilation (TTA-UC) is employed in order to enhance the response of solar cells to sub-bandgap light. Here, we present the first report of an integrated photovoltaic device, combining a dye-sensitized solar cell (DSC) and TTA-UC system. The integrated device displays enhanced current under sub-bandgap illumination, resulting in a figure of merit (FoM) under low concentration (3 suns), which is competitive with the best values recorded to date for nonintegrated systems. Thus, we demonstrate both the compatibility of DSC and TTA-UC and a viable method for device integration.

  17. Hydride stretch infrared spectra in the excited electronic states of indole and its derivatives: Direct evidence for the 1πσ* state

    NASA Astrophysics Data System (ADS)

    Dian, Brian C.; Longarte, Asier; Zwier, Timothy S.

    2003-02-01

    The hydride stretch infrared spectra of indole, indole-H2O, 3-methyl indole, 3-methyl indole-H2O, the main conformer of tryptamine (TRA), two conformers of N-acetyl tryptophan amide (NATA), and three conformers of N-acetyl tryptophan methyl amide (NATMA), have been recorded in the electronically excited singlet states using excited-state fluorescence-dip infrared spectroscopy. NATA and NATMA are methyl-capped dipeptides of tryptophan that have conformational flexibility and exhibit sensitivity in their electronic spectra to the conformation of the dipeptide backbone. In the indole monomer, the indole NH stretch fundamental at the S1 origin is shifted from its ground-state value (3525 cm-1) to 3478 cm-1. The corresponding band in the indole-H2O complex appears at 3387 cm-1, shifted by a similar amount from its ground-state position (3436 cm-1). Higher vibronic levels within 1500 cm-1 of the S1 origin, which have been identified previously [B. J. Fender et al., Chem. Phys. Lett. 239, 31 (1995)] as being 1Lb or 1La in character, all show similar excited state indole NH stretch absorptions. The corresponding spectra in 3-methyl indole, 3-methyl indole-H2O, TRA, and in the C5 conformers of NATA and NATMA all are missing the indole NH stretch absorption. In its place, a broad background absorption appears, spread over the entire 2800-3800 cm-1 region. In these molecules, other CH stretch or amide NH stretch absorptions remain sharp, appearing in their expected frequency ranges. Finally, the C7 conformations of NATA and NATMA, which possess an intramolecular hydrogen bond in the dipeptide backbone, have all infrared transitions washed out, replaced by a stronger broad background absorption. The entire data set can be explained by the presence of an excited 1πσ* state which is dissociative along the indole NH stretch coordinate, as recently predicted by Sobolewski and Domcke [Chem. Phys. Lett. 315, 293 (1999)]. In the weak coupling case (indole, indole-H2O), the gap

  18. The protein's role in triplet energy transfer in bacterial reaction centers.

    SciTech Connect

    Laible, P. D.

    1998-08-14

    When photosynthetic organisms are subjected to high-light conditions in nature, electron transfer becomes blocked as the rate of conversion of light into charge-separated states in the reaction center (RC) exceeds the capacity of the soluble carriers involved in cyclic electron transfer. In that event, a well-characterized T{sub 0}-polarized triplet state {sup T}P, is formed on the primary donor, P, from the P{sup +}H{sub A}{sup {minus}} state (reviewed in [1]). In an aerobic or semi-aerobic environment, the major role of the carotenoid (C), also bound by the RC, is to quench {sup T}P prior to its sensitization of the {sup 1}{Delta}{sub g} singlet state of oxygen--a potentially damaging biological oxidant. The carotenoid performs this function efficiently in most bacterial RCs by rapidly accepting the triplet state from P and dissipating this excited-state energy into heat through internal conversion. The lowest-lying triplet states of P and the carotenoid are sufficiently different that {sup T}P can promote oxygen to its excited singlet state whereas {sup T}C can quench the {sup T}P state (reviewed in [2]).

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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

  4. 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

  5. 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

  6. FT-IR and FT-Raman spectra of 5-fluoroorotic acid with solid state simulation by DFT methods

    NASA Astrophysics Data System (ADS)

    Cuellar, A.; Alcolea Palafox, M.; Rastogi, V. K.; Kiefer, W.; Schlücker, S.; Rathor, S. K.

    2014-11-01

    FT-Raman and FT-IR studies of the biomolecule 5-fluoroorotic acid in the solid state were carried out. The unit cell found in the crystal was simulated as a tetramer form by density functional calculations. They were performed to clarify wavenumber assignments of the experimental observed bands in the spectra. Correlations with the molecule of uracil were made, and specific scale equations were employed to scale the wavenumbers of 5-fluoroorotic acid. Good reproduction of the experimental wavenumbers is obtained and the % error is very small in the majority of the bands. This fact confirms our simplified solid state model. The molecular structure was fully optimized using DFT and MP2 methods. The relative stability of both the syn and anti conformations was investigated, and the anti-form was found to be slightly more stable, by 7.49 kJ/mol at the MP2 level. The structures of all possible tautomeric forms were determined. The keto-form appeared as the most stable one. The NBO atomic charges and several thermodynamic parameters were also calculated.

  7. 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.

  8. 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)

  9. Resistively detected NMR spectra of the crystal states of the two-dimensional electron gas in a quantizing magnetic field

    NASA Astrophysics Data System (ADS)

    Côté, R.; Simoneau, Alexandre M.

    2016-02-01

    Transport experiments on the two-dimensional electron gas (2DEG) confined into a semiconductor quantum well and subjected to a quantizing magnetic field have uncovered a rich variety of uniform and nonuniform phases such as the Laughlin liquids, the Wigner, bubble, and Skyrme crystals, and the quantum Hall stripe state. Optically pumped nuclear magnetic resonance (OP-NMR) has also been extremely useful in studying the magnetization and dynamics of electron solids with exotic spin textures such as the Skyrme crystal. Recently, it has been demonstrated that a related technique, resistively-detected nuclear magnetic resonance (RD-NMR), could be a good tool to study the topography of the electron solids in the fractional and integer quantum Hall regimes. In this work, we compute theoretically the RD-NMR line shapes of various crystal phases of the 2DEG and study the relation between their spin density and texture and their NMR spectra. This allows us to evaluate the ability of the RD-NMR to discriminate between the various types of crystal states.

  10. Consistency of the triplet seesaw model revisited

    NASA Astrophysics Data System (ADS)

    Bonilla, Cesar; Fonseca, Renato M.; Valle, J. W. F.

    2015-10-01

    Adding a scalar triplet to the Standard Model is one of the simplest ways of giving mass to neutrinos, providing at the same time a mechanism to stabilize the theory's vacuum. In this paper, we revisit these aspects of the type-II seesaw model pointing out that the bounded-from-below conditions for the scalar potential in use in the literature are not correct. We discuss some scenarios where the correction can be significant and sketch the typical scalar boson profile expected by consistency.

  11. Quasiparticle energies, excitons, and optical spectra of few-layer black phosphorus

    NASA Astrophysics Data System (ADS)

    Tran, Vy; Fei, Ruixiang; Yang, Li

    2015-12-01

    We report first-principles GW-Bethe-Salpeter-equation (BSE) studies of excited-state properties of few-layer black phosphorus (BP) (phosphorene). With improved GW computational methods, we obtained converged quasiparticle band gaps and optical absorption spectra by the single-shot (G0W0) procedure. Moreover, we reveal fine structures of anisotropic excitons, including the series of one-dimensional like wave functions, spin singlet-triplet splitting, and electron-hole binding energy spectra by solving BSE. An effective-mass model is employed to describe these electron-hole pairs, shedding light on estimating the exciton binding energy of anisotropic two-dimensional semiconductors without expensive ab initio simulations. Finally, the anisotropic optical response of BP is explained by using optical selection rules based on the projected single-particle density of states at band edges.

  12. 1/f-like spectra in cortical and subcortical brain structures: A possible marker of behavioral state-dependent self-organization

    NASA Astrophysics Data System (ADS)

    Anderson, C. M.; Holroyd, T.; Bressler, S. L.; Selz, K. A.; Mandell, A. J.; Nakamura, R.

    1993-08-01

    Recently, power-law scaling of power spectra with scaling exponents close to -1 (1/f-like spectra) have been observed in cortical and subcortical brain structures in association with specific behavioral states. Further, 1/f processes at different levels of organization have been reported in the nervous systems of vertebrates and invertebrates. This study describes the 1/f-like appearance of cross-spectra between cortical sites in a monkey performing a GO/NO-GO behavioral task. We found broadband 1/f-like coherence spectra (average slope =-0.84) during the ``behaviorally flexible'' state of tonic arousal shortly after the monkey had initiated the trial, suggesting that this brain state is characterized by long-range cortical correlations. One of the implications of these findings is that the 1/f-like cortical coherence spectra may provide a signature of brain self-organization during specific behavioral states. A more general implication is that broadband 1/f-like processes across many levels of organization in the nervous system may provide a versatile and parsimonious mechanism for binding cortical and subcortical nonlinear oscillators rapidly and specifically to environmental information.

  13. 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).

  14. 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

  15. Far infrared spectra of solid state L-serine, L-threonine, L-cysteine, and L-methionine in different protonation states.

    PubMed

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

    2015-01-01

    In this study, experimental far infrared measurements of L-serine, L-threonine, L-cysteine, and L-methionine are presented showing the spectra for the 1.0-13.0 pH range. In parallel, solid state DFT calculations were performed on the amino acid zwitterions in the crystalline form. We focused on the lowest frequency far infrared normal modes, which required the most precision and convergence of the calculations. Analysis of the computational results, which included the potential energy distribution of the vibrational modes, permitted a detailed and almost complete assignment of the experimental spectrum. In addition to characteristic signals of the two main acid-base couples, CO2H/CO2(-) and NH3(+)/NH2, specific side chain contributions for these amino acids, including CCO and CCS vibrational modes were analyzed. This study is in line with the growing application of FIR measurements to biomolecules.

  16. 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

  17. Ab initio calculations of optical spectra by solving the Bethe-Salpeter equation without empty states.Work

    NASA Astrophysics Data System (ADS)

    Rocca, Dario; Lu, Deyu; Galli, Giulia

    2009-03-01

    We present a novel first principle approach to solve the Bethe-Salpeter equation (BSE) that builds on recent progress in time-dependent density functional perturbation theory [1], and uses an eigenvalue decomposition representation of the dielectric matrix [2]. This approach does not require the explicit calculation of excited single particle electronic states, making it suitable for calculations involving large basis sets and/or a large number of transitions. The numerical solution of the BSE is obtained through a generalized, non-Hermitian Lanczos iterative algorithm and does not require the use of the Tamm-Dancoff approximation. Furthermore, since Lanczos coefficients are frequency independent, optical spectra may be obtained in a very broad energy range. The efficiency and accuracy of the new approach are demonstrated by calculating the optical properties of silicon nanoclusters with up to 1 nm diameter. [1] D. Rocca, R. Gebauer, Y Saad, and S. Baroni, J. Chem. Phys. 128, 154105 (2008). [2] H.Wilson, F.Gygi and G.Galli, Phys. Rev. B 78, 113303 (2008).

  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. 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

  20. Noise filtering of composite pulses for singlet-triplet qubits

    NASA Astrophysics Data System (ADS)

    Yang, Xu-Chen; Wang, Xin

    2016-07-01

    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.

  1. 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.

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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

  7. 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.

  8. 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

  9. Assignment of phantom bands in the solid-state infrared and Raman spectra of coronene: The importance of a minute out-of-plane distortion.

    PubMed

    Todorov, Petar D; Jenneskens, Leonardus W; van Lenthe, Joop H

    2010-01-21

    The molecular geometry and the normal modes properties of coronene are investigated by means of DFT(B3LYP) and restricted/Hartree-Fock calculations utilizing basis sets of triple zeta+polarization quality. The interpretation of the infrared and Raman spectra of coronene, especially in solid state, is critically revised. The phantom bands in the solid state, previously not understood, are readily assigned after considering a minute out-of-plane molecular distortion from D(6h) to C(2h).

  10. Lowest electronic states of the CP47 antenna protein complex of photosystem II: simulation of optical spectra and revised structural assignments.

    PubMed

    Reppert, Mike; Acharya, Khem; Neupane, Bhanu; Jankowiak, Ryszard

    2010-09-16

    In this work, we present simulated steady-state absorption, emission, and nonresonant hole burning (HB) spectra for the CP47 antenna complex of photosystem II (PS II) based on fits to recently refined experimental data (Neupane et al. J. Am. Chem. Soc. 2010, 132, 4214). Excitonic simulations are based on the 2.9 Å resolution structure of the PS II core from cyanobacteria (Guskov et al. Nat. Struct. Mol. Biol. 2009, 16, 334), and allow for preliminary assignment of the chlorophylls (Chls) contributing to the lowest excitonic states. The search for realistic site energies was guided by experimental constraints and aided by simple fitting algorithms. The following experimental constraints were used: (i) the oscillator strength of the lowest-energy state should be approximately ≤0.5 Chl equivalents; (ii) the excitonic structure must explain the experimentally observed red-shifted (∼695 nm) emission maximum; and (iii) the excitonic interactions of all states must properly describe the broad (non-line-narrowed, NLN) HB spectrum (including its antihole) whose shape is extremely sensitive to the excitonic structure of the complex, especially the lowest excitonic states. Importantly, our assignments differ significantly from those previously reported by Raszewski and Renger (J. Am. Chem. Soc. 2008, 130, 4431), due primarily to differences in the experimental data simulated. In particular, we find that the lowest state localized on Chl 526 possesses too high of an oscillator strength to fit low-temperature experimental data. Instead, we suggest that Chl 523 most strongly contributes to the lowest excitonic state, with Chl 526 contributing to the second excitonic state. Since the fits of nonresonant holes are more restrictive (in terms of possible site energies) than those of absorption and emission spectra, we suggest that fits of linear optical spectra along with HB spectra provide more realistic site energies.

  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.

  12. Formation of Schiff-base for photoreaction mechanism of red shift of GFP spectra.

    PubMed

    Koseki, Jun; Kita, Yukiumi; Tachikawa, Masanori

    2010-04-01

    We have proposed the formation of Schiff-base between R96 and chromophore (CRO) to elucidate the reaction mechanism for the irreversible red shift of green fluorescent protein (GFP) spectra under the absence of oxygen. The difference between absorption energies of reactant and product for our GFP models with CIS(D)/6-31G* level is 0.21eV, which is in reasonable agreement with the corresponding experimental value of 0.25eV. We have suggested the irreversible photoreaction mechanism, where the CRO excited from ground (S(0)) state to first excited singlet (S(1)) state immediately turns to the first excited triplet (T(1)) state, and the nucleophilic addition reaction occurs on the T(1) state.

  13. 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.

  14. Tunnelling splittings in the high resolution microwave and UV spectra of the benzonitrile-water complex: modelling the internal motion in its S 0 and S 1 states

    NASA Astrophysics Data System (ADS)

    Schafer, Martin; Borst, David R.; Pratt, David W.; Brendel, Kai

    Refined values of the barriers to internal motion in the 1:1 complex between benzonitrile and water in the gas phase have been determined from analyses of its fully resolved microwave and ultraviolet spectra. Both spectra exhibit tunnelling splittings associated with this motion. Modelling this behaviour using a semi-rigid Hamiltonian for an internal rotation of water around its C 2 axis yields values of V 2 = 440 ±30cm -1 and 450 ±30cm -1 in the ground and excited electronic states, respectively. These relatively high barriers are a consequence of two hydrogen bonds between the interacting species.

  15. 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

  16. Singlet-triplet annihilation limits exciton yield in poly(3-hexylthiophene).

    PubMed

    Steiner, Florian; Vogelsang, Jan; Lupton, John M

    2014-04-01

    Control of chain length and morphology in combination with single-molecule spectroscopy techniques provides a comprehensive photophysical picture of excited-state losses in the prototypical conjugated polymer poly(3-hexylthiophene) (P3HT). Our examination reveals a universal self-quenching mechanism, based on singlet-triplet exciton annihilation, which accounts for the dramatic loss in fluorescence quantum yield of a single P3HT chain between its solution (unfolded) and bulklike (folded) state. Triplet excitons fundamentally limit the fluorescence of organic photovoltaic materials, which impacts the conversion of singlet excitons to separated charge carriers, decreasing the efficiency of energy harvested at high excitation densities. Interexcitonic interactions are so effective that a single P3HT chain of order 100  kDa weight behaves like a 2-level system, exhibiting perfect photon antibunching. PMID:24745453

  17. Two-photon absorption spectra of a near-infrared 2-azaazulene polymethine dye: solvation and ground-state symmetry breaking.

    PubMed

    Hu, Honghua; Przhonska, Olga V; Terenziani, Francesca; Painelli, Anna; Fishman, Dmitry; Ensley, Trenton R; Reichert, Matthew; Webster, Scott; Bricks, Julia L; Kachkovski, Alexey D; Hagan, David J; Van Stryland, Eric W

    2013-05-28

    Polymethine dyes (PDs) with absorption bands in the near-infrared region undergo symmetry breaking in polar solvents. To investigate how symmetry breaking affects nonlinear optical responses of PDs, an extensive and challenging experimental characterization of a cationic 2-azaazulene polymethine dye, including linear absorption, fluorescence, two-photon absorption and excited-state absorption, has been performed in two solvents with different polarity. Based on this extensive set of experimental data, a three-electronic-state model, accounting for the coupling of electronic degrees of freedom to molecular vibrations and polar solvation, has been reliably parameterized and validated for this dye, fully rationalizing optical spectra in terms of spectral position, intensities and bandshapes. In low-polarity solvents where the dye is mainly in its symmetric form, a nominally forbidden two-photon absorption band is observed, due to a vibronic activation mechanism. Inhomogeneous broadening plays a major role in polar solvents: absorption spectra represent the weighted sum of contributions from states with a variable amount of symmetry breaking, leading to a complex evolution of linear and nonlinear optical spectra with solvent polarity. In more polar solvents, the dominant role of the asymmetric form leads to the activation of two-photon absorption as a result of the symmetry lowering. The subtle interplay between the two mechanisms for two-photon absorption activation, vibronic coupling and polar solvation, can be fully accounted for within the proposed microscopic model allowing a detailed interpretation of the optical spectra of PDs.

  18. 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.

  19. ATOMIC AND MOLECULAR PHYSICS: Theoretical analysis of ionic autoionization spectra of lanthanum via an intermediate state [Xe]5d6d 1P1

    NASA Astrophysics Data System (ADS)

    Zhong, Yin-Peng; Jia, Feng-Dong; Zhong, Zhi-Ping

    2009-10-01

    In the framework of multi-channel quantum defect theory, eigenquantum defects μα and the transformation matrices Uiα of La+ are calculated from first principles by relativistic multi-channel theory, while the dipole matrix elements Dα are obtained by fitting with experimental data. Then the ionic autoionization spectra of lanthanum via the intermediate state [Xe]5d6d 1P1 in the energy region of 90213-91905 cm-1 are obtained. Experimental peaks are classified and assigned by comparing with the corresponding calculated spectra. More specifically, four ionic autoionization Rydberg series converging to La2+ 5d5/2 2D5/2 and several states converging to higher lying states of La2+ are found and assigned.

  20. 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.

  1. 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.

  2. Infrared spectra and theoretical calculations for Fe, Ru, and Os metal hydrides and dihydrogen complexes.

    PubMed

    Wang, Xuefeng; Andrews, Lester

    2009-01-22

    Laser-ablated iron, ruthenium, and osmium atoms react with hydrogen in excess argon, neon and pure hydrogen to produce the FeH(2) molecule, and the FeH(2)(H(2))(3), RuH(H(2))(4), RuH(2)(H(2))(4), and (H(2))MH complexes (M = Fe, Ru, Os), as identified through infrared spectra with D(2) and HD substitution. DFT frequency calculations support the assignment of absorptions observed experimentally. The FeH(2) molecule has a quintet ground state with a quasi-linear structure, and is repulsive to the addition of one more H(2) ligand: however, with three more H(2) ligands, stable triplet and singlet state FeH(2)(H(2))(3) supercomplexes can be formed. The quintet FeH(2) molecule and FeH(2)(H(2))(3) supercomplex undergo reversible near-ultraviolet photochemical rearrangement in solid neon and hydrogen. The RuH(2) molecule has a bent triplet ground state and forms the stable singlet RuH(2)(H(2))(4) supercomplex, but only the latter is observed in these experiments. In like fashion RuH has a quartet ground state and the doublet RuH(H(2))(4) complex is trapped in solid hydrogen. All three (H(2))MH complexes with lower energy than MH(3) are trapped, and no absorptions are observed for MH(3) molecules.

  3. Infrared spectra and theoretical calculations for Fe, Ru, and Os metal hydrides and dihydrogen complexes.

    PubMed

    Wang, Xuefeng; Andrews, Lester

    2009-01-22

    Laser-ablated iron, ruthenium, and osmium atoms react with hydrogen in excess argon, neon and pure hydrogen to produce the FeH(2) molecule, and the FeH(2)(H(2))(3), RuH(H(2))(4), RuH(2)(H(2))(4), and (H(2))MH complexes (M = Fe, Ru, Os), as identified through infrared spectra with D(2) and HD substitution. DFT frequency calculations support the assignment of absorptions observed experimentally. The FeH(2) molecule has a quintet ground state with a quasi-linear structure, and is repulsive to the addition of one more H(2) ligand: however, with three more H(2) ligands, stable triplet and singlet state FeH(2)(H(2))(3) supercomplexes can be formed. The quintet FeH(2) molecule and FeH(2)(H(2))(3) supercomplex undergo reversible near-ultraviolet photochemical rearrangement in solid neon and hydrogen. The RuH(2) molecule has a bent triplet ground state and forms the stable singlet RuH(2)(H(2))(4) supercomplex, but only the latter is observed in these experiments. In like fashion RuH has a quartet ground state and the doublet RuH(H(2))(4) complex is trapped in solid hydrogen. All three (H(2))MH complexes with lower energy than MH(3) are trapped, and no absorptions are observed for MH(3) molecules. PMID:19099441

  4. Physical properties and spectra of IO, IO- and HOI studied by ab initio methods.

    PubMed

    Minaev, Boris; Loboda, Oleksandr; Vahtras, Olav; Agren, Hans; Bilan, Elena

    2002-03-15

    Structure and properties of the IO, IO- and HOI species, which are of potential importance for the ozone destruction catalytic cycle in the troposphere, have been calculated together with the EPR, NMR and UV-visible spectra by ab initio methodology with account of spin-orbit coupling (SOC) effects. Multi-configuration self-consistent field calculations with linear and quadratic response techniques and the multi-reference configuration interaction method have been employed. Photodissociation of these species, crucial for the catalytic ozone-destruction cycle, is critically reviewed and analyzed. Calculations predict that the singlet-triplet (S-T) transition to the lowest triplet state (X1 A' --> 3A'') should be responsible for the weak long-wavelength tail absorption (approximately 450-560 nm) and photodissociation of the HOI molecule. The second, more intense, band around 400 nm is produced by two overlapping S-S and S-T transitions. In order to check this assignment of the HOI photodissociation the isoelectronic IO- anion and IO radical have been studied by the same methods. Comparison with the EPR spectrum of the IO radical indicates that the methods are reliable which gives credit to the accuracy of the HOI spectral interpretation. NMR spectra of HOI and IO- molecules and some other properties are calculated for the first time.

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

    PubMed Central

    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

  6. Discordant sex in one of three monozygotic triplets.

    PubMed Central

    Dallapiccola, B; Stomeo, C; Ferranti, G; Di Lecce, A; Purpura, M

    1985-01-01

    A case is reported of monozygotic triplets, discordant for phenotypic sex, in which the female presented at birth with the features of Turner's syndrome. Chromosomal analyses showed homogeneous 46,XY karyotypes in the lymphocytes of the three sibs, while a 45,X non-mosaic chromosome constitution was detected in skin fibroblasts of the female triplet. It is suggested that mitotic non-disjunction or anaphase lag occurring early during embryonic development accounted for the occurrence of monosomy X in one cell line of the affected triplet. Previous observations of monozygotic twin pairs discordant for chromosome constitutions are reviewed. Images PMID:3856681

  7. Two-Gap Superconductivity in LaNiGa_{2} with Nonunitary Triplet Pairing and Even Parity Gap Symmetry.

    PubMed

    Weng, Z F; Zhang, J L; Smidman, M; Shang, T; Quintanilla, J; Annett, J F; Nicklas, M; Pang, G M; Jiao, L; Jiang, W B; Chen, Y; Steglich, F; Yuan, H Q

    2016-07-01

    The nature of the pairing states of superconducting LaNiC_{2} and LaNiGa_{2} has to date remained a puzzling question. Broken time reversal symmetry has been observed in both compounds and a group theoretical analysis implies a nonunitary triplet pairing state. However, all the allowed nonunitary triplet states have nodal gap functions but most thermodynamic and NMR measurements indicate fully gapped superconductivity in LaNiC_{2}. Here we probe the gap symmetry of LaNiGa_{2} by measuring the London penetration depth, specific heat, and upper critical field. These measurements demonstrate two-gap nodeless superconductivity in LaNiGa_{2}, suggesting that this is a common feature of both compounds. These results allow us to propose a novel triplet superconducting state, where the pairing occurs between electrons of the same spin, but on different orbitals. In this case the superconducting wave function has a triplet spin component but isotropic even parity gap symmetry, yet the overall wave function remains antisymmetric under particle exchange. This model leads to a nodeless two-gap superconducting state which breaks time reversal symmetry, and therefore accounts well for the seemingly contradictory experimental results.

  8. Two-Gap Superconductivity in LaNiGa2 with Nonunitary Triplet Pairing and Even Parity Gap Symmetry

    NASA Astrophysics Data System (ADS)

    Weng, Z. F.; Zhang, J. L.; Smidman, M.; Shang, T.; Quintanilla, J.; Annett, J. F.; Nicklas, M.; Pang, G. M.; Jiao, L.; Jiang, W. B.; Chen, Y.; Steglich, F.; Yuan, H. Q.

    2016-07-01

    The nature of the pairing states of superconducting LaNiC2 and LaNiGa2 has to date remained a puzzling question. Broken time reversal symmetry has been observed in both compounds and a group theoretical analysis implies a nonunitary triplet pairing state. However, all the allowed nonunitary triplet states have nodal gap functions but most thermodynamic and NMR measurements indicate fully gapped superconductivity in LaNiC2 . Here we probe the gap symmetry of LaNiGa2 by measuring the London penetration depth, specific heat, and upper critical field. These measurements demonstrate two-gap nodeless superconductivity in LaNiGa2 , suggesting that this is a common feature of both compounds. These results allow us to propose a novel triplet superconducting state, where the pairing occurs between electrons of the same spin, but on different orbitals. In this case the superconducting wave function has a triplet spin component but isotropic even parity gap symmetry, yet the overall wave function remains antisymmetric under particle exchange. This model leads to a nodeless two-gap superconducting state which breaks time reversal symmetry, and therefore accounts well for the seemingly contradictory experimental results.

  9. Two-Gap Superconductivity in LaNiGa_{2} with Nonunitary Triplet Pairing and Even Parity Gap Symmetry.

    PubMed

    Weng, Z F; Zhang, J L; Smidman, M; Shang, T; Quintanilla, J; Annett, J F; Nicklas, M; Pang, G M; Jiao, L; Jiang, W B; Chen, Y; Steglich, F; Yuan, H Q

    2016-07-01

    The nature of the pairing states of superconducting LaNiC_{2} and LaNiGa_{2} has to date remained a puzzling question. Broken time reversal symmetry has been observed in both compounds and a group theoretical analysis implies a nonunitary triplet pairing state. However, all the allowed nonunitary triplet states have nodal gap functions but most thermodynamic and NMR measurements indicate fully gapped superconductivity in LaNiC_{2}. Here we probe the gap symmetry of LaNiGa_{2} by measuring the London penetration depth, specific heat, and upper critical field. These measurements demonstrate two-gap nodeless superconductivity in LaNiGa_{2}, suggesting that this is a common feature of both compounds. These results allow us to propose a novel triplet superconducting state, where the pairing occurs between electrons of the same spin, but on different orbitals. In this case the superconducting wave function has a triplet spin component but isotropic even parity gap symmetry, yet the overall wave function remains antisymmetric under particle exchange. This model leads to a nodeless two-gap superconducting state which breaks time reversal symmetry, and therefore accounts well for the seemingly contradictory experimental results. PMID:27447519

  10. The Moving Lines on Electron Spectra as Charge Reflexes on Non-equilibrium States of Nanostructured Surfaces.

    PubMed

    Mishchuk, Oleg A

    2016-12-01

    The experimental results present the phenomenon of moving lines on electron spectra which are linked spatially and in time with the localization and durability of the processes of new surface producing in folds and grain boundaries. This effect was also realized for a thin-layer composite "organic on metal films on dielectric substrate" in modeling non-equilibrium conditions which are created by the intensive electron beam pulse impact. It was found that the nature of the inceptive adsorption layer, in addition to the metal film, determines the initial positions of moving lines on the spectra. The main accents in these investigations were in observations of appearance of the moving lines, dynamics of their displacements on the spectra, final stages when these lines vanished, and finding the general regularities between the spontaneous and induced events.

  11. The Moving Lines on Electron Spectra as Charge Reflexes on Non-equilibrium States of Nanostructured Surfaces

    NASA Astrophysics Data System (ADS)

    Mishchuk, Oleg A.

    2016-04-01

    The experimental results present the phenomenon of moving lines on electron spectra which are linked spatially and in time with the localization and durability of the processes of new surface producing in folds and grain boundaries. This effect was also realized for a thin-layer composite "organic on metal films on dielectric substrate" in modeling non-equilibrium conditions which are created by the intensive electron beam pulse impact. It was found that the nature of the inceptive adsorption layer, in addition to the metal film, determines the initial positions of moving lines on the spectra. The main accents in these investigations were in observations of appearance of the moving lines, dynamics of their displacements on the spectra, final stages when these lines vanished, and finding the general regularities between the spontaneous and induced events.

  12. The Moving Lines on Electron Spectra as Charge Reflexes on Non-equilibrium States of Nanostructured Surfaces.

    PubMed

    Mishchuk, Oleg A

    2016-12-01

    The experimental results present the phenomenon of moving lines on electron spectra which are linked spatially and in time with the localization and durability of the processes of new surface producing in folds and grain boundaries. This effect was also realized for a thin-layer composite "organic on metal films on dielectric substrate" in modeling non-equilibrium conditions which are created by the intensive electron beam pulse impact. It was found that the nature of the inceptive adsorption layer, in addition to the metal film, determines the initial positions of moving lines on the spectra. The main accents in these investigations were in observations of appearance of the moving lines, dynamics of their displacements on the spectra, final stages when these lines vanished, and finding the general regularities between the spontaneous and induced events. PMID:27083583

  13. Collisionally-Mediated Singlet-Triplet Crossing in ˜{a}1A1 CH_2 Revisited: (010) Coupling

    NASA Astrophysics Data System (ADS)

    Le, Anh T.; Hall, Gregory; Sears, Trevor

    2014-06-01

    Methylene, CH2, possesses a ground ˜{X}3B1 ground electronic state and an excited ˜{a}1A1 state only 3150cm-1 higher in energy. The collision-induced singlet-triplet crossing in the gaseous mixtures is important in determining overall reaction rates and chemical behavior. Accidental near-degeneracies between rotational levels of the singlet state and the vibrationally excited triplet state result in a few gateway rotational levels that mediate collision-induced intersystem crossing. The mixed states can be recognized and quantified by deperturbation, knowing the zero-order singlet and triplet energy levels. Hyperfine structure can be used as alternative indicator of singlet-triplet mixing. Non-zero mixing will induce hyperfine splittings intermediate between the unresolved hyperfine structure of pure singlet and the resolvable (≈50MHz) splittings of pure triplet, arising from the (I\\cdotS) interaction in the ortho states, where nuclear spin I=1. Collision-induced intersystem crossing rates from the (010) state are comparable to those for (000), yet the identities and characters of the presumed gateway states are unknown. A new spectrometer is under construction to investigate triplet mixing rotational levels of ˜{a}1A1(010) by sub-Doppler measurements of perturbation-induced hyperfine splittings. Their observation will permit the identification of gateway states and quantification of the degree of triplet contamination of the singlet wavefunction. Progress in the measurements and the analysis of rotational energy transfer in (010) will be reported. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. C.-H. Chang, G. E. Hall, T. J. Sears, J. Chem. Phys 133, 144310(2010) G. E. Hall, A. V. Komissarov, and T. J. Sears, J. Phys. Chem. A 108 7922-7927 (2004)

  14. Direct measurements of the current-phase relation in long-range spin-triplet SFS Josephson junctions

    NASA Astrophysics Data System (ADS)

    Hamilton, David; van Harlingen, Dale; Wang, Yixing; Birge, Norman

    2015-03-01

    We present direct measurements of the current-phase relation (CPR) of Josephson junctions which use multiple ferromagnetic layers to generate long-range spin-triplet pair correlations. Using a phase-sensitive Josephson interferometry technique, we obtain the phase and temperature dependence of this spin-triplet supercurrent. We also demonstrate the use of an inductive shunt to enhance this technique at higher critical currents. Our data suggest that the current-phase relation of these junctions is harmonic in character. Further measurements are planned in order to determine the ground state phase shift of these junctions.

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

    SciTech Connect

    Corona, Maria; Garay-Palmett, Karina; U'Ren, Alfred B.

    2011-09-15

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

  16. Theory of Triplet Excitation Transfer in the Donor-Oxygen-Acceptor System: Application to Cytochrome b6f.

    PubMed

    Petrov, Elmar G; Robert, Bruno; Lin, Sheng Hsien; Valkunas, Leonas

    2015-10-20

    Theoretical consideration is presented of the triplet excitation dynamics in donor-acceptor systems in conditions where the transfer is mediated by an oxygen molecule. It is demonstrated that oxygen may be involved in both real and virtual intramolecular triplet-singlet conversions in the course of the process under consideration. Expressions describing a superexchange donor-acceptor coupling owing to a participation of the bridging twofold degenerate oxygen's virtual singlet state are derived and the transfer kinetics including the sequential (hopping) and coherent (distant) routes are analyzed. Applicability of this theoretical description to the pigment-protein complex cytochrome b6f, by considering the triplet excitation transfer from the chlorophyll a molecule to distant β-carotene, is discussed. PMID:26488665

  17. Magnetic field effects on the decay rate of photogenerated biradical from intramolecular electron transfer of triplet excited fullerene in a fullerene phenothiazine linked compound

    NASA Astrophysics Data System (ADS)

    Yonemura, Hiroaki; Tokudome, Hiromasa; Yamada, Sunao

    2001-10-01

    Transient absorption spectra of a fullerene (C 60)-phenothiazine (PH) linked compound indicated that the intramolecular electron transfer occurred in benzonitrile, while not in benzene. In benzonitrile, the lifetime (118 ns) of photogenerated biradical was very long, in spite of being around the top region in Marcus theory. The lifetime of the biradical was enhanced by 1.8 times in the presence of magnetic fields (>0.2 T). The magnetic field effects verified that the triplet biradical was generated from the intramolecular electron transfer from PH to the triplet C 60. The long lifetime is most likely ascribed to spin multiplicities of the biradical.

  18. Comparative assessment of density functional methods for evaluating essential parameters to simulate SERS spectra within the excited state energy gradient approximation

    NASA Astrophysics Data System (ADS)

    Mohammadpour, Mozhdeh; Jamshidi, Zahra

    2016-05-01

    The prospect of challenges in reproducing and interpretation of resonance Raman properties of molecules interacting with metal clusters has prompted the present research initiative. Resonance Raman spectra based on the time-dependent gradient approximation are examined in the framework of density functional theory using different methods for representing the exchange-correlation functional. In this work the performance of different XC functionals in the prediction of ground state properties, excitation state energies, and gradients are compared and discussed. Resonance Raman properties based on time-dependent gradient approximation for the strongly low-lying charge transfer states are calculated and compared for different methods. We draw the following conclusions: (1) for calculating the binding energy and ground state geometry, dispersion-corrected functionals give the best performance in comparison to ab initio calculations, (2) GGA and meta GGA functionals give good accuracy in calculating vibrational frequencies, (3) excited state energies determined by hybrid and range-separated hybrid functionals are in good agreement with EOM-CCSD calculations, and (4) in calculating resonance Raman properties GGA functionals give good and reasonable performance in comparison to the experiment; however, calculating the excited state gradient by using the hybrid functional on the hessian of GGA improves the results of the hybrid functional significantly. Finally, we conclude that the agreement of charge-transfer surface enhanced resonance Raman spectra with experiment is improved significantly by using the excited state gradient approximation.

  19. Epigenetics and Triplet-Repeat Neurological Diseases

    PubMed Central

    Nageshwaran, Sathiji; Festenstein, Richard

    2015-01-01

    The term “junk DNA” has been reconsidered following the delineation of the functional significance of repetitive DNA regions. Typically associated with centromeres and telomeres, DNA repeats are found in nearly all organisms throughout their genomes. Repetitive regions are frequently heterochromatinized resulting in silencing of intrinsic and nearby genes. However, this is not a uniform rule, with several genes known to require such an environment to permit transcription. Repetitive regions frequently exist as dinucleotide, trinucleotide, and tetranucleotide repeats. The association between repetitive regions and disease was emphasized following the discovery of abnormal trinucleotide repeats underlying spinal and bulbar muscular atrophy (Kennedy’s disease) and fragile X syndrome of mental retardation (FRAXA) in 1991. In this review, we provide a brief overview of epigenetic mechanisms and then focus on several diseases caused by DNA triplet-repeat expansions, which exhibit diverse epigenetic effects. It is clear that the emerging field of epigenetics is already generating novel potential therapeutic avenues for this group of largely incurable diseases. PMID:26733936

  20. Epigenetics and Triplet-Repeat Neurological Diseases.

    PubMed

    Nageshwaran, Sathiji; Festenstein, Richard

    2015-01-01

    The term "junk DNA" has been reconsidered following the delineation of the functional significance of repetitive DNA regions. Typically associated with centromeres and telomeres, DNA repeats are found in nearly all organisms throughout their genomes. Repetitive regions are frequently heterochromatinized resulting in silencing of intrinsic and nearby genes. However, this is not a uniform rule, with several genes known to require such an environment to permit transcription. Repetitive regions frequently exist as dinucleotide, trinucleotide, and tetranucleotide repeats. The association between repetitive regions and disease was emphasized following the discovery of abnormal trinucleotide repeats underlying spinal and bulbar muscular atrophy (Kennedy's disease) and fragile X syndrome of mental retardation (FRAXA) in 1991. In this review, we provide a brief overview of epigenetic mechanisms and then focus on several diseases caused by DNA triplet-repeat expansions, which exhibit diverse epigenetic effects. It is clear that the emerging field of epigenetics is already generating novel potential therapeutic avenues for this group of largely incurable diseases. PMID:26733936

  1. Scalar triplet on a domain wall: an exact solution

    NASA Astrophysics Data System (ADS)

    Gani, Vakhid A.; Lizunova, Mariya A.; Radomskiy, Roman V.

    2016-04-01

    We study a model with a real scalar Higgs field and a scalar triplet field that allows existence of a topological defect — a domain wall. The wall breaks the global O(3) symmetry of the model, which gives rise to non-Abelian orientational degrees of freedom. We found an exact analytic solution that describes a domain wall with a localized configuration of the triplet field on it. This solution enables one to calculate contributions to the action from the orientational and translational degrees of freedom of the triplet field. We also study the linear stability of the domain wall with the triplet field switched off. We obtain that degrees of freedom localized on the wall can appear or do not appear depending on the parameters of the model.

  2. Effects of Ferromagnetic Nanowires on Singlet and Triplet Exciton Fractions in Fluorescent and Phosphorescent Organic Semiconductors

    SciTech Connect

    Hu, Bin; Wu, Yue; Zhang, Zongtao; Dai, Sheng; Shen, Jian

    2006-01-01

    We report a magnetic field-dependent electroluminescence (EL) induced by ferromagnetic Co{sub 53}Pt{sub 47} nanowires in fluorescent conjugated polymer poly[2-methoxy-5-(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene] and phosphorescent iridium-complex Ir(ppy){sub 3} molecules. The photoluminescence and EL studies indicate that the dispersed CoPt nanowires increase the singlet-to-triplet exciton ratio in organic semiconductors, suggesting that the spin-polarized holes were injected into the organic molecules from the CoPt nanowires under electrical excitation. Therefore, the use of ferromagnetic nanomaterials demonstrates a pathway to tune the optoelectronic properties that are related to singlet and triplet states in organic semiconducting materials.

  3. Distance-Dependent Triplet Energy Transfer between CdSe Nanocrystals and Surface Bound Anthracene.

    PubMed

    Li, Xin; Huang, Zhiyuan; Zavala, Ramsha; Tang, Ming Lee

    2016-06-01

    We investigate triplet energy transfer (TET) across variable-length aromatic oligo-p-phenylene and aliphatic bridges in a covalently linked CdSe nanocrystal (NC)-bridge-anthracene hybrid system. Photon upconversion measurements in saturated 9,10-diphenylanthracene hexane solutions under air-free conditions at room temperature provided the steady-state rate of TET (ket) across this interface. For flexible transmitters, ket is similar for different lengths of aliphatic bridges, suggesting that the ligands bend backward. For the rigid phenylene spacer, triplet sensitization of anthracene transmitter molecules by CdSe NCs shows a strong distance dependence, with a Dexter damping coefficient of 0.43 ± 0.07 Å(-1). The anthracene transmitter bound closest to the NC surface gave the highest quantum yield of 14.3% for the conversion of green to violet light, the current record for a hybrid platform. PMID:27164056

  4. Spin-triplet supercurrent in Co/Ni multilayer Josephson junctions with perpendicular anisotropy

    NASA Astrophysics Data System (ADS)

    Gingrich, E. C.; Quarterman, P.; Wang, Yixing; Loloee, R.; Pratt, W. P., Jr.; Birge, Norman O.

    2012-12-01

    We have measured spin-triplet supercurrent in Josephson junctions of the form S/F'/F/F'/S, where S is superconducting Nb, F' is a thin Ni layer with in-plane magnetization, and F is a Ni/[Co/Ni]n multilayer with out-of-plane magnetization. The supercurrent in these junctions decays very slowly with F-layer thickness and is much larger than in similar junctions not containing the two F' layers. Those two features are the characteristic signatures of spin-triplet supercurrent, which is maximized by the orthogonality of the magnetizations in the F and F' layers. Magnetic measurements confirm the out-of-plane anisotropy of the Co/Ni multilayers. These samples have their critical current optimized in the as-prepared state, which will be useful for future applications.

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

    PubMed Central

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

    2016-01-01

    A strategy for increasing the conversion efficiency of organic photovoltaics has been to increase the VOC by tuning the energy levels of donor and acceptor components. However, this opens up a new loss pathway from an interfacial charge transfer state to a triplet exciton (TE) state called electron back transfer (EBT), which is detrimental to device performance. To test this hypothesis, we study triplet formation in the high performing PTB7:PC71BM blend system and determine the impact of the morphology-optimizing additive 1,8-diiodoctane (DIO). Using photoluminescence and spin-sensitive optically detected magnetic resonance (ODMR) measurements at low temperature, we find that TEs form on PC71BM via intersystem crossing from singlet excitons and on PTB7 via EBT mechanism. For DIO blends with smaller fullerene domains, an increased density of PTB7 TEs is observed. The EBT process is found to be significant only at very low temperature. At 300 K, no triplets are detected via ODMR, and electrically detected magnetic resonance on optimized solar cells indicates that TEs are only present on the fullerenes. We conclude that in PTB7:PC71BM devices, TE formation via EBT is impacted by fullerene domain size at low temperature, but at room temperature, EBT does not represent a dominant loss pathway. PMID:27380928

  6. Triplet superconductivity in 3D Dirac semi-metal due to exchange interaction.

    PubMed

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

    2015-01-21

    Conventional phonon-electron interaction induces either triplet or one of two (degenerate) singlet pairing states in time reversal and inversion invariant 3D Dirac semi-metal. Investigation of the order parameters and energies of these states at zero temperature in a wide range of values of chemical potential μ, the effective electron-electron coupling constant λ and Debye energy TD demonstrates that when the exchange interaction is neglected the singlet always prevails, however, in significant portions of the (μ, λ, TD) parameter space the energy difference is very small. This means that interactions that are small, but discriminate between the spin singlet and the spin triplet, are important in order to determine the nature of the superconducting order there. The best candidate for such an interaction in the materials under consideration is the exchange (the Stoner term) characterized by constant λex. We show that at values of λex, much smaller than ones creating Stoner instability to ferromagnetism λex ∼ 1, the triplet pairing becomes energetically favored over the singlet ones. The 3D quantum critical point at μ = 0 is considered in detail. This can be realized experimentally in optically trapped cold atom systems. PMID:25501668

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    PubMed

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

    2016-07-06

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

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

    PubMed

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

    2016-01-01

    A strategy for increasing the conversion efficiency of organic photovoltaics has been to increase the VOC by tuning the energy levels of donor and acceptor components. However, this opens up a new loss pathway from an interfacial charge transfer state to a triplet exciton (TE) state called electron back transfer (EBT), which is detrimental to device performance. To test this hypothesis, we study triplet formation in the high performing PTB7:PC71BM blend system and determine the impact of the morphology-optimizing additive 1,8-diiodoctane (DIO). Using photoluminescence and spin-sensitive optically detected magnetic resonance (ODMR) measurements at low temperature, we find that TEs form on PC71BM via intersystem crossing from singlet excitons and on PTB7 via EBT mechanism. For DIO blends with smaller fullerene domains, an increased density of PTB7 TEs is observed. The EBT process is found to be significant only at very low temperature. At 300 K, no triplets are detected via ODMR, and electrically detected magnetic resonance on optimized solar cells indicates that TEs are only present on the fullerenes. We conclude that in PTB7:PC71BM devices, TE formation via EBT is impacted by fullerene domain size at low temperature, but at room temperature, EBT does not represent a dominant loss pathway. PMID:27380928

  10. Triplet superconductivity in 3D Dirac semi-metal due to exchange interaction

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    Conventional phonon-electron interaction induces either triplet or one of two (degenerate) singlet pairing states in time reversal and inversion invariant 3D Dirac semi-metal. Investigation of the order parameters and energies of these states at zero temperature in a wide range of values of chemical potential μ, the effective electron-electron coupling constant λ and Debye energy TD demonstrates that when the exchange interaction is neglected the singlet always prevails, however, in significant portions of the (μ, λ, TD) parameter space the energy difference is very small. This means that interactions that are small, but discriminate between the spin singlet and the spin triplet, are important in order to determine the nature of the superconducting order there. The best candidate for such an interaction in the materials under consideration is the exchange (the Stoner term) characterized by constant λex. We show that at values of λex, much smaller than ones creating Stoner instability to ferromagnetism λex ˜ 1, the triplet pairing becomes energetically favored over the singlet ones. The 3D quantum critical point at μ = 0 is considered in detail. This can be realized experimentally in optically trapped cold atom systems.

  11. Nanostructured singlet fission photovoltaics subject to triplet-charge annihilation.

    PubMed

    Thompson, Nicholas J; Hontz, Eric; Congreve, Daniel N; Bahlke, Matthias E; Reineke, Sebastian; Van Voorhis, Troy; Baldo, Marc A

    2014-03-01

    Singlet exciton fission is an efficient multiple-exciton generation process that is vulnerable to a characteristic loss process: triplet-charge annihilation. This loss process is characterized in singlet-fission photovoltaics and losses as high as 40% are observed in poorly designed devices. Techniques are demonstrated to improve charge extraction and reduce triplet-charge annihilation to negligible levels at short-circuit conditions. PMID:24281738

  12. Production and installation of the LHC low-beta triplets

    SciTech Connect

    Feher, S.; Bossert, R.; DiMarco, J.; Karppinen, M.; Kerby, J.; Kimura, N.; Lamm, M.J.; Nakamoto, T.; Nicol, T.; Nobrega, A.; Ogitsu, T.; Ohuchi, N.; Ostojic, R.; Page, T.; Peterson, T.; Rabehl, R.; Schlabach, P.; Shintomi, T.; Strait, J.; Sylvester, C.; Tartaglia, M.; /Fermilab /CERN /KEK, Tsukuba

    2005-09-01

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

  13. Thickness dependence of the triplet spin-valve effect in superconductor–ferromagnet–ferromagnet heterostructures

    PubMed Central

    Zdravkov, Vladimir I; Kehrle, Jan-Michael; Obermeier, Günter; Ullrich, Aladin; Morari, Roman; Krug von Nidda, Hans-Albrecht; Müller, Claus; Kupriyanov, Mikhail Yu; Sidorenko, Anatolie S; Horn, Siegfried; Deminov, Rafael G; Tagirov, Lenar R; Tidecks, Reinhard

    2016-01-01

    Summary Background: In nanoscale layered S/F1/N/F2/AF heterostructures, the generation of a long-range, odd-in-frequency spin-projection one triplet component of superconductivity, arising at non-collinear alignment of the magnetizations of F1 and F2, exhausts the singlet state. This yields the possibility of a global minimum of the superconducting transition temperature T c, i.e., a superconducting triplet spin-valve effect, around mutually perpendicular alignment. Results: The superconducting triplet spin valve is realized with S = Nb a singlet superconductor, F1 = Cu41Ni59 and F2 = Co ferromagnetic metals, AF = CoOx an antiferromagnetic oxide, and N = nc-Nb a normal conducting (nc) non-magnetic metal, which serves to decouple F1 and F2. The non-collinear alignment of the magnetizations is obtained by applying an external magnetic field parallel to the layers of the heterostructure and exploiting the intrinsic perpendicular easy-axis of the magnetization of the Cu41Ni59 thin film in conjunction with the exchange bias between CoOx and Co. The magnetic configurations are confirmed by superconducting quantum interference device (SQUID) magnetic moment measurements. The triplet spin-valve effect has been investigated for different layer thicknesses, d F1, of F1 and was found to decay with increasing d F1. The data is described by an empirical model and, moreover, by calculations using the microscopic theory. Conclusion: The long-range triplet component of superconducting pairing is generated from the singlet component mainly at the N/F2 interface, where the amplitude of the singlet component is suppressed exponentially with increasing distance d F1. The decay length of the empirical model is found to be comparable to twice the electron mean free path of F1 and, thus, to the decay length of the singlet component in F1. Moreover, the obtained data is in qualitative agreement with the microscopic theory, which, however, predicts a (not investigated) breakdown of the

  14. Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Basavaraja, Jana; Suresh Kumar, H. M.; Inamdar, S. R.; Wari, M. N.

    2016-02-01

    The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π → π* transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μe). It is observed that dipole moment value of excited state (μe) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state.

  15. Phonon density of states of Sn in textured SnO under high pressure: Comparison of nuclear inelastic x-ray scattering spectra to a shell model

    SciTech Connect

    Giefers, H.; Koval, S.; Wortmann, G.; Sturhahn, W.; Alp, E. E.; Hu, M. Y.

    2006-09-01

    The local phonon density of states (DOS) at the Sn site in tin monoxide (SnO) is studied at pressures up to 8 GPa with {sup 119}Sn nuclear resonant inelastic x-ray scattering (NRIXS) of synchrotron radiation at 23.88 keV. The preferred orientation (texture) of the SnO crystallites in the investigated samples is used to measure NRIXS spectra preferentially parallel and almost perpendicular to the c axis of tetragonal SnO. A subtraction method is applied to these NRIXS spectra to produce projected local Sn DOS spectra as seen parallel and perpendicular to the c axis of SnO. These experimentally obtained local Sn DOS spectra, both in the polycrystalline case as well as projected parallel and perpendicular to the c axis, are compared with corresponding theoretical phonon DOS spectra, derived from dispersion relations calculated with a recently developed shell model. Comparison between the experimental projected Sn DOS spectra and the corresponding theoretical DOS spectra enables us to follow the pressure-induced shifts of several acoustic and optic phonon modes. While the principal spectral features of the experimental and theoretical phonon DOS agree well at energies above 10 meV, the pressure behavior of the low-energy part of the DOS is not well reproduced by the theoretical calculations. In fact, they exhibit, in contrast to the experimental data, a dramatic softening of two low-energy modes, their energies approaching zero around 2.5 GPa, clearly indicating the limitations of the applied shell model. These difficulties are obviously connected with the complex Sn-O and Sn-Sn bindings within and between the Sn-O-Sn layers in the litharge structure of SnO. We derived from the experimental and theoretical DOS spectra a variety of elastic and thermodynamic parameters of the Sn sublattice, such as the Lamb-Moessbauer factor, the mean force constant, and Debye temperatures, as well as the vibrational contributions to the Helmholtz free energy, specific heat, entropy, and

  16. Resonance fluorescence spectra from coherently driven quantum dots coupled to slow-light photonic crystal waveguides

    NASA Astrophysics Data System (ADS)

    Roy-Choudhury, Kaushik; Mann, Nishan; Manson, Ross; Hughes, Stephen

    2016-06-01

    Using a polaron master equation approach, we investigate the resonance fluorescence spectra from coherently driven quantum dots (QDs) coupled to an acoustic phonon bath and photonic crystal waveguides with a rich local density of photon states (LDOS). Resonance fluorescence spectra from QDs in semiconductor crystals are known to show strong signatures of electron-phonon interactions, but when coupled to a structured photonic reservoir, the QD emission properties are also determined by the frequency dependence of the LDOS of the photon reservoir. Here, we investigate the simultaneous role of coupled photon and phonon baths on the characteristic Mollow triplet spectra from a strongly driven QD. As an example structured photonic reservoir, we first study a photonic crystal coupled cavity waveguide, and find that photons and phonons have counterinteracting effects near the upper mode edge of the coupled-cavity waveguide, thus establishing the importance of their separate roles in determining the emission spectra. The general theory is developed for arbitrary photonic reservoirs and is further applied to determine the resonance fluorescence spectra from a realistic, disordered W1 photonic crystal waveguide showing important photon-phonon interaction effects that are directly relevant to emerging experiments and theoretical proposals.

  17. Imaging the radical channel in acetaldehyde photodissociation: Competing mechanisms at energies close to the triplet exit barrier

    SciTech Connect

    Amaral, G. A.; Arregui, A.; Rodriguez, J. D.; Banares, L.; Rubio-Lago, L.

    2010-08-14

    The photodissociation of acetaldehyde in the radical channel has been studied at wavelengths between 315 and 325 nm using the velocity-map imaging technique. Upon one-photon absorption at 315 nm, the molecule is excited to the first singlet excited state S{sub 1}, which, in turn, undergoes intersystem crossing to the first excited triplet state T{sub 1}. On the triplet surface, the molecule dissociates into CH{sub 3} and HCO radicals with large kinetic energy release (KER), in accordance with the well characterized exit barrier on T{sub 1}. However, at longer wavelengths (>320 nm), which correspond to excitation energies just below the triplet barrier, a sudden change in KER is observed. At these photolysis wavelengths, there is not enough energy to surpass the exit barrier on the triplet state, which leaves the possibility of unimolecular dissociation on S{sub 0} after internal conversion from S{sub 1}. We have characterized the fragments' KER at these wavelengths, as well as determined the energy partitioning for the radical fragments. A new accurate estimate of the barrier height on T{sub 1} is presented.

  18. Transport of triplet excitons along continuous 100 nm polyfluorene chains

    SciTech Connect

    Xi, Liang; Bird, Matthew; Mauro, Gina; Asaoka, Sadayuki; Cook, Andrew R.; Chen, Hung -Cheng; Miller, John R.

    2014-12-03

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

  19. Transport of triplet excitons along continuous 100 nm polyfluorene chains

    DOE PAGESBeta

    Xi, Liang; Bird, Matthew; Mauro, Gina; Asaoka, Sadayuki; Cook, Andrew R.; Chen, Hung -Cheng; Miller, John R.

    2014-12-03

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

  20. Solvent effects on the absorption and fluorescence spectra of quinine sulphate: Estimation of ground and excited-state dipole moments

    NASA Astrophysics Data System (ADS)

    Joshi, Sunita; Pant, Debi D.

    2012-06-01

    Ground and excited state dipole moments of probe quinine sulphate (QS) was obtained using Solvatochromic shift method. Higher dipole moment is observed for excited state as compared to the ground state which is attributed to the higher polarity of excited state.

  1. The {ital T}{sub 1}({ital n}{pi}{asterisk}){l_arrow}{ital S}{sub 0} laser induced phosphorescence excitation spectrum of acetaldehyde in a supersonic free jet: Torsion and wagging potentials in the lowest triplet state

    SciTech Connect

    Liu, H.; Lim, E.C.; Munoz-Caro, C.; Nino, A.; Judge, R.H.; Moule, D.C.

    1996-08-01

    The laser induced {ital T}{sub 1}({ital n}{pi}{asterisk}){l_arrow}{ital S}{sub 0} phosphorescence excitation spectrum of jet-cooled acetaldehyde has been observed for the first time with a rotating slit nozzle excitation system. The vibronic origins were fitted to a set of levels that were obtained from a Hamiltonian that employed flexible torsion-wagging large amplitude coordinates. The potential surface extracted from the fitting procedure yielded barriers to torsion and inversion of 609.68 and 869.02 cm{sup {minus}1}, respectively. Minima in the potential hypersurface at {theta}=61.7{degree} and {alpha}=42.2{degree} defined the equilibrium positions for the torsion and wagging coordinates. A comparison to the corresponding {ital S}{sub 1}-state parameters showed that the torsion barrier (in cm{sup {minus}1}) does not greatly change, {ital S}{sub 1}/{ital T}{sub 1}=710.8/609.7, whereas the barrier height for the wagging-inversion barrier increases dramatically, 574.4/869.0. {copyright} {ital 1996 American Institute of Physics.}

  2. Low-spin states of /sup 250/Cf populated in the electron capture decay of 2. 22-h /sup 250/Es. [ULTIPOLE TRANSITIONS; PARITY; ROTATIONAL STATES; SPIN; VIBRATIONAL STATES; GAMMA SPECTRA

    SciTech Connect

    Ahmad, I.; Sjoblom, R.K.

    1980-09-01

    Low-spin states of /sup 250/Cf have been investigated by measuring ..gamma.. rays and conversion electrons associated with the electron capture decay of 2.22-h /sup 250/Es. Mass-separated /sup 250/Es samples produced by the /sup 249/Cf(d,n) reaction were used for these measurements. The ..gamma..-ray spectra were measured with a 25-cm/sup 3/ coaxial Ge(Li) spectrometer and the electron spectra were measured with a cooled Si(Li) detector. Multipolarities of intense transitions in /sup 250/Cf were deduced and logft values of electron capture transitions were derived from measured electron capture intensities. On the basis of the results of the present investigation the following bandheads were identified in /sup 250/Cf: E (keV),K,I..pi..=871.6, 2,2-; 1031.9, 2,2+; 1154.2, 0,0+; 1175.5, 1,1-; 1210.0, 2,2-; 1244.4, 2,2+; 1266.5, 0,0+; and 1658.1, 2,2+. The 2.22-h state in /sup 250/Es has been given a spin-parity assignment of 1- with configuration )n(734)9/2-; p(633)7/2+)/sub 1//sub -/.

  3. Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

    SciTech Connect

    Fujihashi, Yuta; Ishizaki, Akihito; Fleming, Graham R.

    2015-06-07

    Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. In this work, we address a dimer which produces little beating of electronic origin in the absence of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.

  4. Identification of redundant and synergetic circuits in triplets of electrophysiological data

    NASA Astrophysics Data System (ADS)

    Erramuzpe, Asier; Ortega, Guillermo J.; Pastor, Jesus; de Sola, Rafael G.; Marinazzo, Daniele; Stramaglia, Sebastiano; Cortes, Jesus M.

    2015-12-01

    Objective. Neural systems are comprised of interacting units, and relevant information regarding their function or malfunction can be inferred by analyzing the statistical dependencies between the activity of each unit. While correlations and mutual information are commonly used to characterize these dependencies, our objective here is to extend interactions to triplets of variables to better detect and characterize dynamic information transfer. Approach. Our approach relies on the measure of interaction information (II). The sign of II provides information as to the extent to which the interaction of variables in triplets is redundant (R) or synergetic (S). Three variables are said to be redundant when a third variable, say Z, added to a pair of variables (X, Y), diminishes the information shared between X and Y. Similarly, the interaction in the triplet is said to be synergetic when conditioning on Z enhances the information shared between X and Y with respect to the unconditioned state. Here, based on this approach, we calculated the R and S status for triplets of electrophysiological data recorded from drug-resistant patients with mesial temporal lobe epilepsy in order to study the spatial organization and dynamics of R and S close to the epileptogenic zone (the area responsible for seizure propagation). Main results. In terms of spatial organization, our results show that R matched the epileptogenic zone while S was distributed more in the surrounding area. In relation to dynamics, R made the largest contribution to high frequency bands (14-100 Hz), while S was expressed more strongly at lower frequencies (1-7 Hz). Thus, applying II to such clinical data reveals new aspects of epileptogenic structure in terms of the nature (redundancy versus synergy) and dynamics (fast versus slow rhythms) of the interactions. Significance. We expect this methodology, robust and simple, can reveal new aspects beyond pair-interactions in networks of interacting units in other

  5. Aberrant EEG functional connectivity and EEG power spectra in resting state post-traumatic stress disorder: a sLORETA study.

    PubMed

    Imperatori, Claudio; Farina, Benedetto; Quintiliani, Maria Isabella; Onofri, Antonio; Castelli Gattinara, Paola; Lepore, Marta; Gnoni, Valentina; Mazzucchi, Edoardo; Contardi, Anna; Della Marca, Giacomo

    2014-10-01

    The aim of the present study was to explore the modifications of EEG power spectra and EEG connectivity of resting state (RS) condition in patients with post-traumatic stress disorder (PTSD). Seventeen patients and seventeen healthy subjects matched for age and gender were enrolled. EEG was recorded during 5min of RS. EEG analysis was conducted by means of the standardized Low Resolution Electric Tomography software (sLORETA). In power spectra analysis PTSD patients showed a widespread increase of theta activity (4.5-7.5Hz) in parietal lobes (Brodmann Area, BA 7, 4, 5, 40) and in frontal lobes (BA 6). In the connectivity analysis PTSD patients also showed increase of alpha connectivity (8-12.5Hz) between the cortical areas explored by Pz-P4 electrode. Our results could reflect the alteration of memory systems and emotional processing consistently altered in PTSD patients.

  6. Singlet and triplet energy transfer in the peridinin-chlorophyll a-protein from Amphidinium carterae

    SciTech Connect

    Bautista, J.A.; Frank, H.A.; Hiller, R.G.; Sharples, F.P.; Gosztola, D.; Wasielewski, M. |

    1999-04-08

    The spectroscopic properties of peridinin in solution, and the efficiency and dynamics of energy transfer from peridinin to chlorophyll a in the peridinin-chlorophyll-protein (PCP) from Amphidinium carterae, were studied by steady-state absorption, fluorescence, fluorescence excitation, and fast transient optical spectroscopy. Steady-state measurements of singlet energy transfer from peridinin to chlorophyll revealed an 88 {+-} 2% efficiency. Fast-transient absorption experiments showed that the excited S{sub 1} state of peridinin decayed in 13.4 {+-} 0.6 ps in methanol and 3.1 {+-} 0.4 ps in the PCP complex after direct excitation of the carotenoid. The onset of the bleaching of the chlorophyll absorption band at 672 nm, signifying the arrival of the excitation from the carotenoid, occurred in 3.2 {+-} 0.3 ps. These data show that the primary route of energy transfer from peridinin to chlorophyll in the PCP complex is through the S{sub 1} state of peridinin. Nanosecond time-resolved transient optical spectroscopy revealed that chlorophyll triplet states are efficiently quenched by peridinin whose triplet state subsequently decays with a lifetime of 10 {+-} 1 {micro}s in the PCP complex. Close association between the peridinins and chlorophyll, which is clearly evident in the 3-D structure of the PCP complex, along with proper alignment of pigments and energy state matching are responsible for the high efficiencies of the photochemical processes.

  7. Thermodynamic analysis of spectra

    SciTech Connect

    Mitchell, G. E.; Shriner, J. F. Jr.

    2008-04-04

    Although random matrix theory had its initial application to neutron resonances, there is a relative scarcity of suitable nuclear data. The primary reason for this is the sensitivity of the standard measures used to evaluate spectra--the spectra must be essential pure (no state with a different symmetry) and complete (no states missing). Additional measures that are less sensitive to these experimental limitations are of significant value. The standard measure for long range order is the {delta}{sub 3} statistic. In the original paper that introduced this statistic, Dyson and Mehta also attempted to evaluate spectra with thermodynamic variables obtained from the circular orthogonal ensemble. We consider the thermodynamic 'internal energy' and evaluate its sensitivity to experimental limitations such as missing and spurious levels. Monte Carlo simulations suggest that the internal energy is less sensitive to mistakes than is {delta}{sub 3}, and thus the internal energy can serve as a addition to the tool kit for evaluating experimental spectra.

  8. Fast and simple acquisition of solid-state 14N NMR spectra with signal enhancement via population transfer.

    PubMed

    O'Dell, Luke A; Schurko, Robert W

    2009-05-20

    A new approach for the acquisition of static, wideline (14)N NMR powder patterns is outlined. The method involves the use of frequency-swept pulses which serve two simultaneous functions: (1) broad-band excitation of magnetization and (2) signal enhancement via population transfer. The signal enhancement mechanism is described using numerical simulations and confirmed experimentally. This approach, which we call DEISM (Direct Enhancement of Integer Spin Magnetization), allows high-quality (14)N spectra to be acquired at intermediate field strengths in an uncomplicated way and in a fraction of the time required for previously reported methods.

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

    PubMed

    Rohling, Niklas; Russ, Maximilian; Burkard, Guido

    2014-10-24

    The valley degree of freedom in the electronic band structure of silicon, graphene, and other materials is often considered to be an obstacle for quantum computing (QC) based on electron spins in quantum dots. Here we show that control over the valley state opens new possibilities for quantum information processing. Combining qubits encoded in the singlet-triplet subspace of spin and valley states allows for universal QC using a universal two-qubit gate directly provided by the exchange interaction. We show how spin and valley qubits can be separated in order to allow for single-qubit rotations. PMID:25379928

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

    PubMed

    Rohling, Niklas; Russ, Maximilian; Burkard, Guido

    2014-10-24

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

  11. [Neonatal morbidity and hospital mortality of preterm triplets.

    PubMed

    Lamshing-Salinas, Priscilla; Rend Ón-Macías, Mario Enrique; Iglesias-Leboreiro, José; Bernárdez-Zapata, Isabel; Braverman-Bronstein, Ariela

    2013-01-01

    Background: multiple gestations have caused an increase in vulnerable preterm births. Our objective was to analyze neonatal morbidity and mortality in preterm triplets. Methods: we analyzed a cohort of 30 triplets in an obstetrics and gynecology hospital. Data were obtained during pregnancy, childbirth and neonatal period: birth order, sex, weight, height, malformations, advanced resuscitation, assisted ventilation, intraventricular hemorrhage, necrotizing enterocolitis, sepsis, pulmonary hypertension, bronchopulmonary dysplasia, days of hospitalization, and death. Results: 90 infants were analyzed. There was an omphalopagus con-joined twins case; 42 (70 %) had between 30-33 weeks and six between 24-29; 19 (21 %) had low weight for gestational age, and 18 (30 %) had a major malformation; 27 % required ventilatory support, 33 % sepsis, 32 % necrotizing enterocolitis, 21 % pulmonary hypertension, 14 % bronchopulmonary dysplasia and 2 % intraventricular hemorrhage, without statistically significant differences related to the order, presentation at birth, sex and number of placentas and amniotic sacs. Eight 24-week triplets died, four over 28 weeks, and a siamese (p = 38). There was no difference in hospital days between triplets. Conclusions: the triplets mortality is low and mainly associated with extreme prematurity, intrauterine growth restriction and sepsis.

  12. Correcting human heart 31P NMR spectra for partial saturation. Evidence that saturation factors for PCr/ATP are homogeneous in normal and disease states

    NASA Astrophysics Data System (ADS)

    Bottomley, Paul A.; Hardy, Christopher J.; Weiss, Robert G.

    Heart PCr/ATP ratios measured from spatially localized 31P NMR spectra can be corrected for partial saturation effects using saturation factors derived from unlocalized chest surface-coil spectra acquired at the heart rate and approximate Ernst angle for phosphor creatine (PCr) and again under fully relaxed conditions during each 31P exam. To validate this approach in studies of normal and disease states where the possibility of heterogeneity in metabolite T1 values between both chest muscle and heart and normal and disease states exists, the properties of saturation factors for metabolite ratios were investigated theoretically under conditions applicable in typical cardiac spectroscopy exams and empirically using data from 82 cardiac 31P exams in six study groups comprising normal controls ( n = 19) and patients with dilated ( n = 20) and hypertrophic ( n = 5) cardiomyopathy, coronary artery disease ( n = 16), heart transplants ( n = 19), and valvular heart disease ( n = 3). When TR ≪ T1,(PCr), with T1(PCr) ⩾ T1(ATP), the saturation factor for PCr/ATP lies in the range 1.5 ± 0.5, regardless of the T1 values. The precise value depends on the ratio of metabolite T1 values rather than their absolute values and is insensitive to modest changes in TR. Published data suggest that the metabolite T1 ratio is the same in heart and muscle. Our empirical data reveal that the saturation factors do not vary significantly with disease state, nor with the relative fractions of muscle and heart contributing to the chest surface-coil spectra. Also, the corrected myocardial PCr/ATP ratios in each normal or disease state bear no correlation with the corresponding saturation factors nor the fraction of muscle in the unlocalized chest spectra. However, application of the saturation correction (mean value, 1.36 ± 0.03 SE) significantly reduced scatter in myocardial PCr/ATP data by 14 ± 11% (SD) ( p ⩽ 0.05). The findings suggest that the relative T1 values of PCr and ATP are

  13. 2-pyridone: The role of out-of-plane vibrations on the S1<-->S0 spectra and S1 state reactivity

    NASA Astrophysics Data System (ADS)

    Frey, Jann A.; Leist, Roman; Tanner, Christian; Frey, Hans-Martin; Leutwyler, Samuel

    2006-09-01

    The S1↔S0 vibronic spectra of supersonic jet-cooled 2-pyridone [pyridin-2-one (2PY)] and its N-H deuterated isotopomer (d-2PY) have been recorded by two-color resonant two-photon ionization, laser-induced fluorescence and emission, and fluorescence depletion spectroscopies. By combining these methods, the B origin of 2PY at 000+98cm-1 and the bands at +218 and +252cm-1 are identified as overtones of the S1 state out-of-plane vibrations ν1' and ν2', as are the analogous bands of d-2PY. Anharmonic double-minimum potentials are derived for the respective out-of-plane coordinates that predict further ν1' and ν2' overtones and combinations, reproducing ˜80% of the vibronic bands up to 600cm-1 above the 000 band. The fluorescence spectra excited at the electronic origins and the ν1' and ν2' out-of-plane overtone levels confirm these assignments. The S1 nonplanar minima and S1←S0 out-of-plane progressions are in agreement with the determination of nonplanar vibrationally averaged geometries for the 000 and 000+98cm-1 upper states by Held et al. [J. Chem. Phys. 95, 8732 (1991)]. The fluorescence lifetimes of the S1 state vibrations show strong mode dependence: Those of the out-of-plane levels decrease rapidly above 200cm-1 excess vibrational energy, while the in-plane vibrations ν5', ν8', and ν9' have longer lifetimes, although they are above or interspersed with the "dark" out-of-plane states. This is interpreted in terms of an S1' state reaction with a low barrier towards a conical intersection with a prefulvenic geometry. Out-of-plane vibrational states can directly surmount this barrier, whereas in-plane vibrations are much less efficient in this respect. Analysis of the fluorescence spectra allows to identify nine in-plane S0' state fundamentals, overtones of the S0 state ν1″ and ν2″ out-of-plane vibrations, and >30 other overtones and combination bands. The B3LYP /6-311++G(d,p) calculated anharmonic wave numbers are in very good agreement with the

  14. The Character of the Long-Lived State Formed from S_1 of Phenylacetylene

    NASA Astrophysics Data System (ADS)

    Johnson, Philip M.; Sears, Trevor J.

    2013-06-01

    Compared to other small aromatic molecules, phenylacetylene (PA) and benzonitrile exhibit strikingly anomalous photophysics on excitation to the S_1 state. Firstly, products are formed on S_1 excitation of a beam-cooled sample that seem to live indefinitely (as defined by the flight time through the apparatus), while action spectra of their formation mirror the rotationally-resolved absorption spectrum of the monomer. Secondly, the long lived products appear immediately during the nsec. laser pulse rather than build up during the lifetime of the singlet level, as is seen in benzene, for example. The question has therefore arisen: is the long lived product of the S_1 excitation the triplet state, as is assumed in all previous work on other molecules, or is it an isomer of some sort? New pump-probe ionization mass spectroscopy experiments have been performed to study the distribution of fragments and metastable ions produced by PA cation derived from the neutral S_1 state, and from the long-lived species. These combined with other experimental results showing weak long-lived components in both the S_1 fluorescence and pump-probe photoelectron spectra that we interpret as recurrence behavior, definitively show the long-lived state is a triplet state of PA, not an isomer. PA with a singlet-triplet gap of 10000 cm^{-1} is acting like intermediate case molecules with much smaller singlet-triplet gaps such as pyrazine and pyrimidine. Calculations point to the existence of four triplet states of PA at or below the energy of S_1 providing a very large density of vibronic states in which to distribute the energy from singlet-triplet crossing. PA T_1 is calculated to be non-planar, in contrast to what is found in benzene, possibly helping to explain the different photophysics. Acknowledgments: We gratefully acknowledge G. V. Lopez for his contributions to some of the experimental masurements. Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02

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

    PubMed

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

    2015-10-22

    Unusual physicochemical properties of ionic liquids (ILs) open vistas for a variety of new applications. Herewith, we investigate the influence of microviscosity and nanostructuring of ILs on spin dynamics of the dissolved photoexcited molecules. We use two most common ILs [Bmim]PF6 and [Bmim]BF4 (with its close analogue [C10mim]BF4) as solvents and photoexcited Zn tetraphenylporphyrin (ZnTPP) as a probe. Time-resolved electron paramagnetic resonance (TR EPR) is employed to investigate spectra and kinetics of spin-polarized triplet ZnTPP in the temperature range 100-270 K. TR EPR data clearly indicate the presence of two microenvironments of ZnTPP in frozen ILs at 100-200 K, being manifested in different spectral shapes and different spin relaxation rates. For one of these microenvironments TR EPR data is quite similar to those obtained in common frozen organic solvents (toluene, glycerol, N-methyl-2-pyrrolidone). However, the second one favors the remarkably slow relaxation of spin polarization, being much longer than in the case of common solvents. Additional experiments using continuous wave EPR and stable nitroxide as a probe confirmed the formation of heterogeneities upon freezing of ILs and complemented TR EPR results. Thus, TR EPR of photoexcited triplets can be effectively used for probing heterogeneities and nanostructuring in frozen ILs. In addition, the increase of polarization lifetime in frozen ILs is an interesting finding that might allow investigation of short-lived intermediates inaccessible otherwise. PMID:26421723

  16. DNA CTG triplet repeats involved in dynamic mutations of neurologically related gene sequences form stable duplexes

    NASA Technical Reports Server (NTRS)

    Smith, G. K.; Jie, J.; Fox, G. E.; Gao, X.

    1995-01-01

    DNA triplet repeats, 5'-d(CTG)n and 5'-d(CAG)n, are present in genes which have been implicated in several neurodegenerative disorders. To investigate possible stable structures formed by these repeating sequences, we have examined d(CTG)n, d(CAG)n and d(CTG).d(CAG)n (n = 2 and 3) using NMR and UV optical spectroscopy. These studies reveal that single stranded (CTG)n (n > 2) forms stable, antiparallel helical duplexes, while the single stranded (CAG)n requires at least three repeating units to form a duplex. NMR and UV melting experiments show that the Tm increases in the order of [(CAG)3]2 < [(CTG)3]2 << (CAG)3.(CTG)3. The (CTG)3 duplex is stable and exhibits similar NMR spectra in solutions containing 0.1-4 M NaCl and at a pH range from 4.6 to 8.8. The (CTG)3 duplex, which contains multiple-T.T mismatches, displays many NMR spectral characteristics similar to those of B-form DNA. However, unique NOE and 1H-31P coupling patterns associated with the repetitive T.T mismatches in the CTG repeats are discerned. These results, in conjunction with recent in vitro studies suggest that longer CTG repeats may form hairpin structures, which can potentially cause interruption in replication, leading to dynamic expansion or deletion of triplet repeats.

  17. Advanced binary search pattern for impedance spectra classification for determining the state of charge of a lithium iron phosphate cell using a support vector machine

    NASA Astrophysics Data System (ADS)

    Jansen, Patrick; Vollnhals, Michael; Renner, Daniel; Vergossen, David; John, Werner; Götze, Jürgen

    2016-09-01

    Further improvements on the novel method for state of charge (SOC) determination of lithium iron phosphate (LFP) cells based on the impedance spectra classification are presented. A Support Vector Machine (SVM) is applied to impedance spectra of a LFP cell, with each impedance spectrum representing a distinct SOC for a predefined temperature. As a SVM is a binary classifier, only the distinction between two SOC can be computed in one iteration of the algorithm. Therefore a search pattern is necessary. A balanced tree search was implemented with good results. In order to further improvements of the SVM method, this paper discusses two new search pattern, namely a linear search and an imbalanced tree search, the later one based on an initial educated guess. All three search pattern were compared under various aspects like accuracy, efficiency, tolerance of disturbances and temperature dependancy. The imbalanced search tree shows to be the most efficient search pattern if the initial guess is within less than ±5 % SOC of the original SOC in both directions and exhibits the best tolerance for high disturbances. Linear search improves the rate of exact classifications for almost every temperature. It also improves the robustness against high disturbances and can even detect a certain number of false classifications which makes this search pattern unique. The downside is a much lower efficiency as all impedance spectra have to be evaluated while the tree search pattern only evaluate those on the tree path.

  18. Orphan spin operators enable the acquisition of multiple 2D and 3D magic angle spinning solid-state NMR spectra

    PubMed Central

    Gopinath, T.; Veglia, Gianluigi

    2013-01-01

    We propose a general method that enables the acquisition of multiple 2D and 3D solid-state NMR spectra for U-13C, 15N-labeled proteins. This method, called MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), makes it possible to detect four coherence transfer pathways simultaneously, utilizing orphan (i.e., neglected) spin operators of nuclear spin polarization generated during 15N-13C cross polarization (CP). In the MEIOSIS experiments, two phase-encoded free-induction decays are decoded into independent nuclear polarization pathways using Hadamard transformations. As a proof of principle, we show the acquisition of multiple 2D and 3D spectra of U-13C, 15N-labeled microcrystalline ubiquitin. Hadamard decoding of CP coherences into multiple independent spin operators is a new concept in solid-state NMR and is extendable to many other multidimensional experiments. The MEIOSIS method will increase the throughput of solid-state NMR techniques for microcrystalline proteins, membrane proteins, and protein fibrils. PMID:23676036

  19. Analysis of the High-Resolution FT-IR and Millimeter-Wave Spectra of the ν 5= 1 State of CHF 2Cl

    NASA Astrophysics Data System (ADS)

    Klatt, Günter; Graner, Georges; Klee, Stefan; Mellau, Georg; Kisiel, Zbigniew; Pszczółkowski, Lech; Alonso, José Luis; López, Juan Carlos

    1996-07-01

    The infrared and millimeter-wave spectra of isotopically pure chlorodifluoromethane (HCFC-22) have been investigated for the ν 5= 1 excited state. IR spectra of CHF 235Cl were recorded at room temperature with high resolution (0.0021 cm -1, Bruker IFS 120 HR) in the region between 560 and 650 cm -1. The spectral analysis of CHF 2Cl allowed us to assign 7788 lines ( J≤ 70) to the ν 5a/ c-hybrid band (ν 0= 596.3714 cm -1). The millimeter-wave rotational spectrum for the ν 5= 1 state was also assigned and measured in the frequency range 8-340 GHz and J≤ 78. The data set contains 208 transitions. The abundance of experimental data enabled us to perform a simultaneous least-squares fit of IR and MW data to determine most of the molecular parameters describing the excited state. Moreover, we were able to determine approximate band centers for several hot bands in the region, which were not studied in detail.

  20. Orphan spin operators enable the acquisition of multiple 2D and 3D magic angle spinning solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Gopinath, T.; Veglia, Gianluigi

    2013-05-01

    We propose a general method that enables the acquisition of multiple 2D and 3D solid-state NMR spectra for U-13C, 15N-labeled proteins. This method, called MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), makes it possible to detect four coherence transfer pathways simultaneously, utilizing orphan (i.e., neglected) spin operators of nuclear spin polarization generated during 15N-13C cross polarization (CP). In the MEIOSIS experiments, two phase-encoded free-induction decays are decoded into independent nuclear polarization pathways using Hadamard transformations. As a proof of principle, we show the acquisition of multiple 2D and 3D spectra of U-13C, 15N-labeled microcrystalline ubiquitin. Hadamard decoding of CP coherences into multiple independent spin operators is a new concept in solid-state NMR and is extendable to many other multidimensional experiments. The MEIOSIS method will increase the throughput of solid-state NMR techniques for microcrystalline proteins, membrane proteins, and protein fibrils.