On the low lying singlet states of BeO
Bauschlicher, C. W., Jr.; Lengsfield, B. H.; Yarkony, D. R.
1980-01-01
Calculations of the ground and low-lying singlet states of BeO are performed in order to gain an understanding of the techniques needed to treat the excited states of other, more complex, ionic molecules. The MCSCF and CI calculations are based on a Gaussian basis set of slightly better than double zeta plus polarization quality for single configuration descriptions of the states. The calculated X-A and X-B state separations are found to be in agreement with experimental measurements. The 1 Sigma - and 1 Delta states are predicted to lie approximately 40,000 kaysers above the ground state and are identified as the C and D states.The 2 1 Pi state is found to be approximately 15,000 kaysers and the 3 1 Sigma + state is found to be approximately 65,000 kaysers above the ground state.
Disjoint nonclassical hydrocarbons have very unstable lowest-lying singlet states: a PM3 study
Directory of Open Access Journals (Sweden)
Richard Francis Langler
2001-12-01
Full Text Available Earlier workers have suggested that disjoint hydrocarbons have nearly-degenerate lowest-lying singlet and triplet states while non-disjoint (or joint hydrocarbons should be ground-state triplets. PM3 results for an appropriate selection of alternant hydrocarbons are inconsistent with that generalization: disjoint, nonclassical, alternant hydrocarbons show the strongest predilection for triplet ground states.
Purwanto, Wirawan; Krakauer, Henry
2009-01-01
We show that the recently developed phaseless auxiliary-field quantum Monte Carlo (AFQMC) method can be used to study excited states, providing an alternative to standard quantum chemistry methods. The phaseless AFQMC approach, whose computational cost scales as M^3-M^4 with system size M, has been shown to be among the most accurate many-body methods in ground state calculations. For excited states, prevention of collapse into the ground state and control of the Fermion sign/phase problem are accomplished by the approximate phaseless constraint with a trial wave function. Using the challenging C2 molecule as a test case, we calculate the potential energy curves of the ground and two low-lying singlet excited states. The trial wave function is obtained by truncating complete active space wave functions, with no further optimization. The phaseless AFQMC results using a small basis set are in good agreement with exact full configuration interaction calculations, while those using large basis sets are in good ag...
Singlet Ground State Magnetism:
DEFF Research Database (Denmark)
Loidl, A.; Knorr, K.; Kjems, Jørgen;
1979-01-01
The magneticGamma 1 –Gamma 4 exciton of the singlet ground state system TbP has been studied by inelastic neutron scattering above the antiferromagnetic ordering temperature. Considerable dispersion and a pronounced splitting was found in the [100] and [110] directions. Both the band width...... and the splitting increased rapidly as the transition temperature was approached in accordance with the predictions of the RPA-theory. The dispersion is analysed in terms of a phenomenological model using interactions up to the fourth nearest neighbour....
Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Hiroyoshi; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jian-Ping
2005-07-01
Electronic absorption spectra were recorded at room temperature in solutions of carotenoids having different numbers of conjugated double bonds, n = 8-13, including a spheroidene derivatives, neurosporene, spheroidene, lycopene, anhydrorhodovibrin and spirilloxanthin. The vibronic states of 1Bu+(v=0-4), 2Ag-(v=0-3), 3Ag- (0) and 1Bu- (0) were clearly identified. The arrangement of the four electronic states determined by electronic absorption spectroscopy was identical to that determined by measurement of resonance Raman excitation profiles [K. Furuichi et al., Chem. Phys. Lett. 356 (2002) 547] for carotenoids in crystals.
A study of the low-lying singlet and triplet electronic states of chlorophyll A and B
Directory of Open Access Journals (Sweden)
Etinski Mihajlo
2013-01-01
Full Text Available Chlorophylls have been extensively investigated both experimentally and theoretically owing to the fact that they are essential for photosynthesis. We have studied two forms of chlorophyll, chlorophyll a and chlorophyll b, by means of density functional theory. Optimization of S0, S1 and T1 states was performed with the B3-LYP functional. The computed fluorescence lifetimes show good agreement with the available experimental data. The electronic adiabatic energies of S1 and T1 states are 2.09/2.12 and 1.19/1.29 eV for chlorophyll a and chlorophyll b respectively. We discussed the implications of this results on the triplet formation. Also, the calculated vertical ionization potentials shows good agreement with the experimental results. [Projekat Ministarstva nauke Reoublike Srbije, br. 172040
Excited singlet states of "hairpin" polyenes
Froelich, Wolfgang; Dewey, Harry J.; Deger, Hans; Dick, Bernhard; Klingensmith, Kenneth A.; Puettmann, Wilhelm; Vogel, Emanuel; Hohlneicher, Georg; Michl, Josef
1983-01-01
The synthesis and UV-visible, polarized-fluorescence and MCD spectra of 6 U-shaped hairpin polyenes (e.g., I) are reported. Qual. arguments and results of p-electron calcns. permit the identification of 4 excited singlet states and their assignment to mixts. of singly and doubly excited configurations. The hairpin polyenes represent a link between the all-trans-polyenes on the 1 hand and the annulenes and acenes on the other; they have the topol. of the former and a geometry near that of the ...
Semiclassical states on Lie algebras
Energy Technology Data Exchange (ETDEWEB)
Tsobanjan, Artur, E-mail: artur.tsobanjan@gmail.com [King’s College, 133 North River Street, Kingston, Pennsylvania 18702 (United States)
2015-03-15
The effective technique for analyzing representation-independent features of quantum systems based on the semiclassical approximation (developed elsewhere) has been successfully used in the context of the canonical (Weyl) algebra of the basic quantum observables. Here, we perform the important step of extending this effective technique to the quantization of a more general class of finite-dimensional Lie algebras. The case of a Lie algebra with a single central element (the Casimir element) is treated in detail by considering semiclassical states on the corresponding universal enveloping algebra. Restriction to an irreducible representation is performed by “effectively” fixing the Casimir condition, following the methods previously used for constrained quantum systems. We explicitly determine the conditions under which this restriction can be consistently performed alongside the semiclassical truncation.
Filatov, Mikhail A.
2015-10-13
The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.
Magnetic excitons in singlet-ground-state ferromagnets
DEFF Research Database (Denmark)
Birgeneau, R.J.; Als-Nielsen, Jens Aage; Bucher, E.
1971-01-01
The authors report measurements of the dispersion of singlet-triplet magnetic excitons as a function of temperature in the singlet-ground-state ferromagnets fcc Pr and Pr3Tl. Well-defined excitons are observed in both the ferromagnetic and paramagnetic regions, but with energies which are nearly...
Probing scalar coupling differences via long-lived singlet states
DeVience, Stephen J.; Walsworth, Ronald L.; Rosen, Matthew S.
2016-01-01
We probe small scalar coupling differences via the coherent interactions between two nuclear spin singlet states in organic molecules. We show that the spin-lock induced crossing (SLIC) technique enables the coherent transfer of singlet order between one spin pair and another. The transfer is mediated by the difference in syn and anti vicinal or long-range J couplings among the spins. By measuring the transfer rate, we calculate a J coupling difference of 8 ± 2 mHz in phenylalanine-glycine-glycine and 2.57 ± 0.04 Hz in glutamate. We also characterize a coherence between two singlet states in glutamate, which may enable the creation of a long-lived quantum memory.
Probing Scalar Coupling Differences via Long-Lived Singlet States
DeVience, Stephen J; Rosen, Matthew S
2015-01-01
We probe small scalar coupling differences via the coherent interactions between two nuclear spin singlet states in organic molecules. We show that the spin-lock induced crossing (SLIC) technique enables the coherent transfer of singlet order between one spin pair and another. The transfer is mediated by the difference in cis and trans vicinal J couplings among the spins. By measuring the transfer rate, we calculate a J coupling difference of $8 \\pm 2$ mHz in phenylalanine-glycine-glycine and $2.57 \\pm 0.04$ Hz in glutamate. We also characterize a coherence between two singlet states in glutamate, which may enable the creation of a long-lived quantum memory.
Preparation of Nuclear Spin Singlet States using Spin-Lock Induced Crossing
DeVience, Stephen J; Rosen, Matthew S
2013-01-01
We introduce a broadly applicable technique to create nuclear spin singlet states in organic molecules and other many-atom systems. We employ a novel pulse sequence to produce a spin-lock induced crossing (SLIC) of the spin singlet and triplet energy levels, which enables triplet/singlet polarization transfer and singlet state preparation. We demonstrate the utility of the SLIC method by producing a long-lived nuclear spin singlet state on two strongly-coupled proton pairs in the tripeptide molecule phenylalanine-glycine-glycine dissolved in D2O, and by using SLIC to measure the J-couplings, chemical shift differences, and singlet lifetimes of the proton pairs. We show that SLIC is more efficient at creating nearly-equivalent nuclear spin singlet states than previous pulse sequence techniques, especially when triplet/singlet polarization transfer occurs on the same timescale as spin-lattice relaxation.
Distinct properties of the triplet pair state from singlet fission.
Trinh, M Tuan; Pinkard, Andrew; Pun, Andrew B; Sanders, Samuel N; Kumarasamy, Elango; Sfeir, Matthew Y; Campos, Luis M; Roy, Xavier; Zhu, X-Y
2017-07-01
Singlet fission, the conversion of a singlet exciton (S1) to two triplets (2 × T1), may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. This process is believed to involve the correlated triplet pair state (1)(TT). Despite extensive research, the nature of the (1)(TT) state and its spectroscopic signature remain actively debated. We use an end-connected pentacene dimer (BP0) as a model system and show evidence for a tightly bound (1)(TT) state. It is characterized in the near-infrared (IR) region (~1.0 eV) by a distinct excited-state absorption (ESA) spectral feature, which closely resembles that of the S1 state; both show vibronic progressions of the aromatic ring breathing mode. We assign these near-IR spectra to (1)(TT)→Sn and S1→Sn' transitions; Sn and Sn' likely come from the antisymmetric and symmetric linear combinations, respectively, of the S2 state localized on each pentacene unit in the dimer molecule. The (1)(TT)→Sn transition is an indicator of the intertriplet electronic coupling strength, because inserting a phenylene spacer or twisting the dihedral angle between the two pentacene chromophores decreases the intertriplet electronic coupling and diminishes this ESA peak. In addition to spectroscopic signature, the tightly bound (1)(TT) state also shows chemical reactivity that is distinctively different from that of an individual T1 state. Using an electron-accepting iron oxide molecular cluster [Fe8O4] linked to the pentacene or pentacene dimer (BP0), we show that electron transfer to the cluster occurs efficiently from an individual T1 in pentacene but not from the tightly bound (1)(TT) state. Thus, reducing intertriplet electronic coupling in (1)(TT) via molecular design might be necessary for the efficient harvesting of triplets from intramolecular singlet fission.
Tetraphenylhexaazaanthracenes: 16π Weakly Antiaromatic Species with Singlet Ground States.
Constantinides, Christos P; Zissimou, Georgia A; Berezin, Andrey A; Ioannou, Theodosia A; Manoli, Maria; Tsokkou, Demetra; Theodorou, Eleni; Hayes, Sophia C; Koutentis, Panayiotis A
2015-08-21
Tetraphenylhexaazaanthracene, TPHA-1, is a fluorescent zwitterionic biscyanine with a closed-shell singlet ground state. TPHA-1 overcomes its weak 16π antiaromaticity by partitioning its π system into 6π positive and 10π negative cyanines. The synthesis of TPHA-1 is low yielding and accompanied by two analogous TPHA isomers: the deep red, non-charge-separated, quinoidal TPHA-2, and the deep green TPHA-3 that partitions into two equal but oppositely charged 8π cyanines. The three TPHA isomers are compared.
Long-Lived Heteronuclear Spin-Singlet States in Liquids at a Zero Magnetic field
Emondts, M.; Ledbetter, M. P.; Pustelny, S.; Theis, T.; Patton, B.; Blanchard, J. W.; Butler, M. C.; Budker, D.; Pines, A.
2014-02-01
We report an observation of long-lived spin-singlet states in a C-H113 spin pair in a zero magnetic field. In C13-labeled formic acid, we observe spin-singlet lifetimes as long as 37 s, about a factor of 3 longer than the T1 lifetime of dipole polarization in the triplet state. In contrast to common high-field experiments, the observed coherence is a singlet-triplet coherence with a lifetime T2 longer than the T1 lifetime of dipole polarization in the triplet manifold. Moreover, we demonstrate that heteronuclear singlet states formed between a H1 and a C13 nucleus can exhibit longer lifetimes than the respective triplet states even in the presence of additional spins that couple to the spin pair of interest. Although long-lived homonuclear spin-singlet states have been extensively studied, this is the first experimental observation of analogous singlet states in heteronuclear spin pairs.
Low-Lying ππ* States of Heteroaromatic Molecules: A Challenge for Excited State Methods.
Prlj, Antonio; Sandoval-Salinas, María Eugenia; Casanova, David; Jacquemin, Denis; Corminboeuf, Clémence
2016-06-14
The description of low-lying ππ* states of linear acenes by standard electronic structure methods is known to be challenging. Here, we broaden the framework of this problem by considering a set of fused heteroaromatic rings and demonstrate that standard electronic structure methods do not provide a balanced description of the two (typically) lowest singlet state (La and Lb) excitations. While the Lb state is highly sensitive to correlation effects, La suffers from the same drawbacks as charge transfer excitations. We show that the comparison between CIS/CIS(D) can serve as a diagnostic for detecting the two problematic excited states. Standard TD-DFT and even its spin-flip variant lead to inaccurate excitation energies and interstate gaps, with only a double hybrid functional performing somewhat better. The complication inherent to a balanced description of these states is so important that even CC2 and ADC(2) do not necessarily match the ADC(3) reference.
Measuring Long-Lived ^{13}C-Singlet State Lifetimes at Natural Abundance
Claytor, Kevin E; Feng, Yesu; Warren, Warren
2013-01-01
Long-lived singlet states hold the potential to drastically extend the lifetime of hyperpolarization in molecular tracers for in-vivo magnetic resonance imaging (MRI). Such long lived hyperpolarization can be used for elucidation of fundamental metabolic pathways, early diagnosis, and optimization of clinical tests for new medication. All previous measurements of 13C singlet state lifetimes rely on costly and time consuming syntheses of 13C labeled compounds. Here we show that it is possible to determine 13C singlet state lifetimes by detecting the naturally abundant doubly-labeled species. This approach allows for rapid and low cost screening of potential molecular biomarkers bearing long-lived singlet states.
On the low-lying states of TiC
Bauschlicher, C. W., Jr.; Siegbahn, P. E. M.
1984-01-01
The ground and low-lying excited states of TiC are investigated using a CASSCF-externally contracted CI approach. The calculations yield a 3Sigma(+) ground state, but the 1Sigma(+) state is only 780/cm higher and cannot be ruled out. The low-lying states have some triple bond character. The nature of the bonding and origin of the states are discussed.
On the low-lying states of TiC
Bauschlicher, C. W., Jr.; Siegbahn, P. E. M.
1984-01-01
The ground and low-lying excited states of TiC are investigated using a CASSCF-externally contracted CI approach. The calculations yield a 3Sigma(+) ground state, but the 1Sigma(+) state is only 780/cm higher and cannot be ruled out. The low-lying states have some triple bond character. The nature of the bonding and origin of the states are discussed.
Dynamics of the higher lying excited states of cyanine dyes. An ultrafast fluorescence study.
Guarin, Cesar A; Villabona-Monsalve, Juan P; López-Arteaga, Rafael; Peon, Jorge
2013-06-20
The electronic relaxation dynamics of the second singlet excited states of several cyanine dyes was studied through the femtosecond fluorescence up-conversion technique. Our interest in these molecules comes from the potential applications of systems with upper excited singlet states with a long lifetime, which can include electron and energy transfer from the higher lying singlets after one- or two-photon absorption. We studied three series of cyanines with 4-quinolyl, 2-quinolyl, or benzothiazolyl type end groups, each with varying sp(2) carbon conjugation lengths in the methinic bridge. The dynamics after electronic excitation to singlet states above the fluorescent state vary significantly as a function of cyanine structure and conjugation length. In particular, for the 4-quinolyl series the cyanine with an intermediate conjugation length (three methinic carbons) has the slowest S2 decays with lifetimes of 5.4 ps in ethanol and 6.6 ps in ethylene glycol. On the other hand, we observed that the 2-quinolyl family has S2 decay times in the subpicosecond range independent of the conjugation length between the end groups. The slowest internal conversion was observed for the benzothiazolyl type cyanine with five methinic carbons, with an S2 lifetime of 17.3 ps in ethanol. For the planar cyanines of this study we observed for the first time a clear systematic trend in the S2 decay times which closely follow the energy gap law. It was also demonstrated that a slow S2 decay is as well observed upon excitation through degenerate two-photon absorption with near-IR pulses. The present study isolates the most important variables for the design of cyanines with long S2 lifetimes.
Eta bound states in nuclei: a probe of flavour-singlet dynamics
Energy Technology Data Exchange (ETDEWEB)
Steven D. Bass; Anthony W. Thomas
2005-07-01
We argue that eta bound states in nuclei are sensitive to the singlet component in the eta. The bigger the singlet component, the more attraction and the greater the binding. Thus, measurements of eta bound states will yield new information about axial U(1) dynamics and glue in mesons. Eta - etaprime mixing plays an important role in understanding the value of the eta-nucleon scattering length.
Long-lived heteronuclear spin-singlet states in liquids at a zero magnetic field.
Emondts, M; Ledbetter, M P; Pustelny, S; Theis, T; Patton, B; Blanchard, J W; Butler, M C; Budker, D; Pines, A
2014-02-21
We report an observation of long-lived spin-singlet states in a 13C-1H spin pair in a zero magnetic field. In 13C-labeled formic acid, we observe spin-singlet lifetimes as long as 37 s, about a factor of 3 longer than the T1 lifetime of dipole polarization in the triplet state. In contrast to common high-field experiments, the observed coherence is a singlet-triplet coherence with a lifetime T2 longer than the T1 lifetime of dipole polarization in the triplet manifold. Moreover, we demonstrate that heteronuclear singlet states formed between a 1H and a 13C nucleus can exhibit longer lifetimes than the respective triplet states even in the presence of additional spins that couple to the spin pair of interest. Although long-lived homonuclear spin-singlet states have been extensively studied, this is the first experimental observation of analogous singlet states in heteronuclear spin pairs.
The Low-Lying Electronic States of YCu
Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)
1995-01-01
The spectroscopic constants for the singlet and triplet states of YCu below about 15 000 per centimeter are determined using an internally contracted multireference configuration-interaction approach. These calculations are calibrated by studies of fewer states using higher levels of correlation treatment and/or larger basis sets. The computed T(sub e) values and radiative lifetimes are in reasonable agreement with experiment. The calculations confirm the previous experimental assignment for all but one state, where theory helps resolve between two possible assignments.
Lukman, Steven; Chen, Kai; Hodgkiss, Justin M.; Turban, David H. P.; Hine, Nicholas D. M.; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C.; Musser, Andrew J.
2016-12-01
Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.
Mitchell, J P; Johnson, E D; Baby, L T; Kemper, K W; Moro, A M; Peplowski, P N; Volya, A; Wiedenhoever, I
2010-01-01
Excitation functions of elastic and inelastic 7Be+p scattering were measured in the energy range between 1.6 and 2.8 MeV in the c.m. An R-matrix analysis of the excitation functions provides strong evidence for new positive parity states in 8B. A new 2+ state at an excitation energy of 2.55 MeV was observed and a new 0+ state at 1.9 MeV is tentatively suggested. The R-matrix and Time Dependent Continuum Shell Model were used in the analysis of the excitation functions. The new results are compared to the calculations of contemporary theoretical models.
The Low-Lying Electronic States of LiB
Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)
1995-01-01
The spectroscopic constants for the triplet and singlet states of LiB below about 30 000/ cm are determined using an internally contracted multireference configuration interaction approach in conjunction with [6s 5p 3d 2f] atomic natural orbital basis sets. The ground state is (sup 3)Pi as found in previous work. No excited triplet states are found to be ideal for characterizing the ground state; the (1)(sup 3)Sigma(sup -) state has a transition energy that is too small for many experimental approaches and the (2)(sup 3)Pi and (3)(sup 3)Pi states have bond lengths that are significantly longer than the ground state, resulting in transition intensities that are spread out over many vibrational levels of the ground state.
The four-qubit singlet state and decoherence-free subspaces
Cabello, A
2002-01-01
It is pointed out that the recent experimental preparation of the four-qubit singlet state by Weinfurter's group is a fundamental achievement for the encoding of quantum information in decoherence-free (DF) subspaces. This state is the DF state orthogonal to the tensor product of two two-qubit singlet states, whose DF properties were experimentally checked by P. G. Kwiat et al. [Science 290, 498 (2000)], and thus provides the missing state for the simplest nontrivial encoding of quantum information in a DF subspace. An experiment to study this DF subspace is suggested.
Ab initio multi-reference configuration interaction of the low-lying states of the AsP molecule
Institute of Scientific and Technical Information of China (English)
Ling Zhang; Chuanlu Yang; Tingqi Ren; Meishan Wang
2008-01-01
Nine low-lying electronic states of the AsP molecule, including Σ+, Ⅱ, and △ symmetries with singlet, triplet, and quintet spin multiplicities, are studied using multi-reference configuration interaction method.The potential energy curves and the spectroscopic constants of these nine states are determined, and compared with the experimental observed data as well as other theoretical works available at present.Three quintet states are reported for the first time.Furthermore, the analytical potential energy functions of these states are fitted using Murrell-Sorbie function and least square fitting method.
Electron-impact excitation of the low-lying electronic states of formaldehyde
Chutjian, A.
1974-01-01
Electron-impact excitation has been observed at incident electron energies of 10.1 and 20.1 eV to the first five excited electronic states of formaldehyde lying at and below the 1B2 state at 7.10 eV. These excitations include two new transitions in the energy-loss range 5.6-6.2 eV and 6.7-7.0 eV which have been detected for the first time, either through electron-impact excitation or photon absorption. The differential cross sections of these new excitations are given at scattering angles between 15 and 135 deg. These cross-section ratios peak at large scattering angles - a characteristic of triplet - singlet excitations. The design and performance of the electron-impact spectrometer used in the above observations is outlined and discussed.
Zheng, Greg Y.; Rillema, D. Paul; DePriest, Jeff; Woods, Clifton
1998-07-13
Direct access to the triplet emitting state from the ground state is observed for Pt(II) complexes containing heterocyclic (CwedgeC', CwedgeN, NwedgeN') and bis(diphenylphosphino)alkane (PwedgeP') ligands. Extinction coefficients for such transitions are in the range 4-25 M(-)(1) cm(-)(1). Emission quantum yields resulting from singlet-to-triplet excitation are as high as 61-77 times the emission quantum yields resulting from singlet-to-singlet excitation at 296 K. The intersystem crossing quantum yield from the singlet excited state to triplet emitting state is lower than 2% at 296 K but is greatly enhanced at 77 K. The forbidden electronic transition observed for Pt(II) complexes is attributed to result from spin-orbit coupling due to the presence of Pt(II) in the skeleton structure. The importance of excitation spectra on the computation of emission quantum yields is discussed.
Olsen, Seth; Schwarzer, Dirk; Troe, Jürgen; Smith, Sean C
2010-04-01
Recent experiments have revealed the existence of an excited state dissociative mechanism for certain peroxycarbonates, with the demonstration that the lifetime of the excited state matches the picosecond time scale for appearance of nascent carbon dioxide product. The data infer that the photoreaction proceeds via an effectively concerted three-body dissociation within the lifetime of the singlet excited state. Many other arylperoxides decay sequentially via [(aryloxy)carbonyl]oxy radical intermediates on nanosecond-microsecond time scales. Uncertainty as to the lifetime of the excited state relates to the character and the relative energetic ordering of states of the parent molecule, since the spectra and photochemistry imply that low-lying states may exist on each of the aryl, carbonate, and peroxide chemical functionalities. We employ many-body electronic structure calculations to determine the energies and characters of the low-lying valence states of a minimal aryl peroxycarbonate model germane to the above-mentioned experiments, methyl phenyl peroxycarbonate (MPC). Our results indicate that the lowest-lying state is an intrinsically nondissociative aryl pipi* excited state. We identify additional low-lying states that are expected to be dissociative in nature and propose that the time scales observed for the dissociation reaction may correspond to the time scale for transfer of excited state population to these states.
Singlet Ground State Magnetism: III Magnetic Excitons in Antiferromagnetic TbP
DEFF Research Database (Denmark)
Knorr, K.; Loidl, A.; Kjems, Jørgen
1981-01-01
The dispersion of the lowest magnetic excitations of the singlet ground state system TbP has been studied in the antiferromagnetic phase by inelastic neutron scattering. The magnetic exchange interaction and the magnetic and the rhombohedral molecular fields have been determined.......The dispersion of the lowest magnetic excitations of the singlet ground state system TbP has been studied in the antiferromagnetic phase by inelastic neutron scattering. The magnetic exchange interaction and the magnetic and the rhombohedral molecular fields have been determined....
The Low-Lying Electronic States of Mg2(+)
Ricca, Alessandra; Bauschlicher, Charles W., Jr.
1994-01-01
The low-lying doublet and quartet states of Mg+ have been studied using a multireference configuration interaction approach. The effect of inner-shell correlation has been included using the core-polarization potential method. The computed spectroscopic constants, lifetimes, and oscillator strengths should help resolve the difference between the recent experiments and previous theoretical calculations.
Dubey, Archana; Badu, S. R.; Scheicher, R. H.; Sahoo, N.; Pink, R. H.; Schulte, A.; Saha, H. P.; Chow, Lee; Nagamine, K.; Das, T. P.
2008-03-01
The observation of paramagnetic susceptibility [1] in Oxy-Hb from measurements over a broad temperature range has stimulated interest in the occurrence of a low-lying excited triplet state close to the ground singlet state of Oxy-Hb. An earlier theoretical investigation [2] has shown the existence of such a triplet state providing support to the interpretation of the susceptibility data [1]. Support for the low-lying excited triplet state has been augmented recently [3] from microscopic relaxation rate measurements for muon attached to the heme group of Oxy-Hb. We are studying by first principles Hartree-Fock procedure the energies and the electronic wave functions of the ground and triplet states and the quantitative theoretical prediction of muon magnetic hyperfine interaction in room temperature μSR measurements on Oxy-Hb. Results will be presented for hyperfine interactions of muon and other nuclei in Oxy-Hb [1] M.Cerdonio etal. Proc. Nat. Acad. Sci USA 75, 4916(1978). [2] Zalek S. Herman and Gilda H Loew JACS 102, 1815(1980).[ 3] K. Nagamine etal Proc. Jpn. Acad.Ser.B 83,120(2007).
Ran, Niva A; Kuik, Martijn; Love, John A; Proctor, Christopher M; Nagao, Ikuhiro; Bazan, Guillermo C; Nguyen, Thuc-Quyen
2014-11-19
Electroluminescence (EL) from the charge-transfer state and singlet excitons is observed at low applied voltages from high-performing small-molecule bulk-heterojunction solar cells. Singlet emission from the blends emerges upon altering the processing conditions, such as thermal annealing and processing with a solvent additive, and correlates with improved photovoltaic performance. Low-temperature EL measurements are utilized to access the physics behind the singlet emission.
Solving the liar detection problem using the four-qubit singlet state
Cabello, A
2003-01-01
A method for solving the Byzantine generals problem [M. Fitzi, N. Gisin, and U. Maurer, Phys. Rev. Lett. 87, 217901 (2001)] and the liar detection problem [A. Cabello, Phys. Rev. Lett. 89, 100402 (2002)] is introduced. The main advantage of this proposal is that it is based on the four-qubit singlet state recently obtained experimentally by Weinfurter's group.
Soluble and stable heptazethrenebis(dicarboximide) with a singlet open-shell ground state
Sun, Zhe
2011-08-10
A soluble and stable heptazethrene derivative was synthesized and characterized for the first time. This molecule exhibits a singlet biradical character in the ground state, which is the first case among zethrene homologue series. Exceptional stability of this heptazethrenebis(dicarboximide) raises the likelihood of its practical applications in materials science. © 2011 American Chemical Society.
Shi, Lingyan; Rodríguez-Contreras, Adrián; Budansky, Yury; Pu, Yang; Nguyen, Thien An; Alfano, Robert R
2014-06-01
Two-photon (2P) excitation of the second singlet (S₂) state was studied to achieve deep optical microscopic imaging in brain tissue when both the excitation (800 nm) and emission (685 nm) wavelengths lie in the "tissue optical window" (650 to 950 nm). S₂ state technique was used to investigate chlorophyll α (Chl α) fluorescence inside a spinach leaf under a thick layer of freshly sliced rat brain tissue in combination with 2P microscopic imaging. Strong emission at the peak wavelength of 685 nm under the 2P S₂ state of Chl α enabled the imaging depth up to 450 μm through rat brain tissue.
Triplet-singlet conversion in ultracold Cs$_2$ and production of ground state molecules
Bouloufa, Nadia; Aymar, Mireille; Dulieu, Olivier
2010-01-01
We propose a process to convert ultracold metastable Cs$_2$ 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 $A^{1}\\Sigma_{u}^{+} \\sim b ^{3}\\Pi_{u}$ states. Using spectroscopic data and accurate quantum chemistry calculations for Cs$_2$ potential curves and transition dipole moments, we show that this process has a high rate and 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.
Energy Technology Data Exchange (ETDEWEB)
Boyé-Péronne, Séverine; Gauyacq, Dolores [Institut des Sciences Moléculaires d’Orsay, UMR 8214, CNRS and Université Paris-Sud, Bât. 210, F-91405 Orsay Cedex (France); Liévin, Jacques, E-mail: jlievin@ulb.ac.be [Service de Chimie Quantique et Photophysique, Université Libre de Bruxelles, Cpi 160/09, 50 Av. F.D. Roosevelt, B-1050 Bruxelles (Belgium)
2014-11-07
The first quantitative description of the Rydberg and valence singlet electronic states of vinylidene lying in the 0–10 eV region is performed by using large scale ab initio calculations. A deep analysis of Rydberg-valence interactions has been achieved thanks to the comprehensive information contained in the accurate Multi-Reference Configuration Interaction wavefunctions and an original population analysis highlighting the respective role played by orbital and state mixing in such interactions. The present theoretical approach is thus adequate for dealing with larger than diatomic Rydberg systems. The nine lowest singlet valence states have been optimized. Among them, some are involved in strong Rydberg-valence interactions in the region of the Rydberg state equilibrium geometry. The Rydberg states of vinylidene present a great similarity with the acetylene isomer, concerning their quantum defects and Rydberg molecular orbital character. As in acetylene, strong s-d mixing is revealed in the n = 3 s-d supercomplex. Nevertheless, unlike in acetylene, the close-energy of the two vinylidene ionic cores {sup 2}A{sub 1} and {sup 2}B{sub 1} results into two overlapped Rydberg series. These Rydberg series exhibit local perturbations when an accidental degeneracy occurs between them and results in avoided crossings. In addition, some Δl = 1 (s-p and p-d) mixings arise for some Rydberg states and are rationalized in term of electrostatic interaction from the electric dipole moment of the ionic core. The strongest dipole moment of the {sup 2}B{sub 1} cationic state also stabilizes the lowest members of the n = 3 Rydberg series converging to this excited state, as compared to the adjacent series converging toward the {sup 2}A{sub 1} ionic ground state. The overall energies of vinylidene Rydberg states lie above their acetylene counterpart. Finally, predictions for optical transitions in singlet vinylidene are suggested for further experimental spectroscopic
Wenthold, Paul G
2012-01-06
Geometries and energies of the triplet and singlet states of 2-furanylnitrene and 3-furanylnitrene have been calculated by using spin-flip coupled-cluster methods. Calculations with triple-ζ basis sets predict a singlet-triplet splitting of 10.9 kcal/mol for 2-furanylnitrene, 4.5 kcal/mol smaller than that in phenylnitrene. In contrast, the singlet-triplet splitting in 3-furanylnitrene is computed to be 1.9 kcal/mol larger than that in phenylnitrene. The differences in the singlet-triplet splittings for the furanylnitrenes are attributed to the differences in the radical stabilizing abilities of the 2-furanyl- and 3-furanyl-groups compared to a phenyl ring. Comparison of the singlet-triplet splittings of more than 20 substituted aromatic nitrenes and the radical stabilizing ability of the aromatic systems reveals a high degree of correlation between the singlet-triplet splitting and the radical stabilizing ability, indicating that singlet states of aromatic nitrenes are preferentially stabilized by radical stabilizing substituents. The preferential stabilization of the singlet states is attributed to the decrease in electron pair repulsion resulting from increased delocalization of the radical electron.
On the low-lying states of CuO
Bagus, P. S.; Nelin, C. J.; Bauschlicher, C. W., Jr.
1984-01-01
Self consistent field and correlated wave functions have been computed for the ground and for several low-lying states of CuO. The ground state is X(2)PI and the lowest excited state, at approximately 8,000/cm above X(2)PI, is a previously unidentified 2-sigma(+) state. The separation of these states is compared to that for the similar states of KO and is analysed in terms of integrals between orbitals of the separated free ions. A classification of the states of the molecule based on states of Cu(+) and O(-) which leads to a division into manifolds of states arising from Cu(+) 3d(10) and Cu(+) 3d(9) 4s(1) is considered. It is predicted that the state of the 3d(9) 4s(1) manifold are 10,000 to 30,000/cm above the ground state and assign the observed A2-sigma(+) state at 16,500/cm to this manifold.
Indirect predissociation of highly excited singlet states of N2
Directory of Open Access Journals (Sweden)
Heays A.N.
2015-01-01
Full Text Available Indirect predissociation of the b′ 1Σu+(v = 20 level of N2 is studied experimentally by vacuum-ultraviolet photoabsorption employing synchrotron radiation and a Fourier-transform spectrometer, and interpreted with the aid of a quantitative model of interacting 1Πu and 1Σu+, bound and unbound states which solves the coupled Schrödinger equation. An observed rotationally-localised peak in the b′(20 predissociation linewidths is identified by the model as arising from an interaction with a strongly predissociated and unobserved bound level of the mixed c3 1Πu and o3 1Πu Rydberg states. This leads to the dissociation of b′(20 into the continuum of the b 1Πu valence state. The residual observed predissociation of b′ 1Σu+(v = 20 apart from the rotationally-localised peak cannot be explained by a mechanism of 1Πu and 1Σu+ interaction, and must involve states of higher multiplicity.
Lowest energy excited singlet state of isolated cis-hexatriene
Kohler, B.E.; Song, K.; Buma, W.J.
1991-01-01
In a previous letter [J. Chem. Phys. 92, 4622 (1990)] we reported the first observation of the 2 1Ag state of cis-hexatriene in a supersonic jet expansion by using resonance enhanced multiphoton ionization spectroscopy. Here, the vibrational analysis of the 1 1Ag2 1Ag excitation spectrum of cis-hexa
Singlet states and the estimation of eigenstates and eigenvalues of an unknown Controlled-U gate
Hillery, M; Hillery, Mark; Buzek, Vladimir
2001-01-01
We consider several problems that involve finding the eigenvalues and generating the eigenstates of unknown unitary gates. We first examine Controlled-U gates that act on qubits, and assume that we know the eigenvalues. It is then shown how to use singlet states to produce qubits in the eigenstates of the gate. We then remove the assumption that we know the eigenvalues and show how to both find the eigenvalues and produce qubits in the eigenstates. Finally, we look at the case where the unitary operator acts on qutrits and has eigenvalues of 1 and -1, where the eigenvalue 1 is doubly degenerate. The eigenstates are unknown. We are able to use a singlet state to produce a qutrit in the eigenstate corresponding to the -1 eigenvalue.
Luo, Ding
2014-01-01
Polycyclic hydrocarbons (PHs) with a singlet biradical ground state have recently attracted extensive interest in physical organic chemistry and materials science. Replacing the carbon radical center in the open-shell PHs with a more electronegative nitrogen atom is expected to result in the more stable aminyl radical. In this work, two kinetically blocked stable/persistent derivatives (1 and 2) of indolo[2,3-b]carbazole, an isoelectronic structure of the known indeno[2,1-b]fluorene, were synthesized and showed different ground states. Based on variable-temperature NMR/ESR measurements and density functional theory calculations, it was found that the indolo[2,3-b]carbazole derivative 1 is a persistent singlet biradical in the ground state with a moderate biradical character (y0 = 0.269) and a small singlet-triplet energy gap (ΔES-T ≅ -1.78 kcal mol-1), while the more extended dibenzo-indolo[2,3-b]carbazole 2 exhibits a quinoidal closed-shell ground state. The difference can be explained by considering the number of aromatic sextet rings gained from the closed-shell to the open-shell biradical resonance form, that is to say, two for compound 1 and one for compound 2, which determines their different biradical characters. The optical and electronic properties of 2 and the corresponding aromatic precursors were investigated by one-photon absorption, transient absorption and two-photon absorption (TPA) spectroscopies and electrochemistry. Amphoteric redox behaviour, a short excited lifetime and a moderate TPA cross section were observed for 2, which can be correlated to its antiaromaticity and small biradical character. Compound 2 showed high reactivity to protic solvents due to its extremely low-lying LUMO energy level. Unusual oxidative dimerization was also observed for the unblocked dihydro-indolo[2,3-b]carbazole precursors 6 and 11. Our studies shed light on the rational design of persistent aminyl biradicals with tunable properties in the future. This journal
Ultrafast internal conversion of excited cytosine via the lowest pipi electronic singlet state.
Merchán, Manuela; Serrano-Andrés, Luis
2003-07-09
Computational evidence at the CASPT2 level supports that the lowest excited state pipi* contributes to the S1/S0 crossing responsible for the ultrafast decay of singlet excited cytosine. The computed radiative lifetime, 33 ns, is consistent with the experimentally derived value, 40 ns. The nOpi* state does not play a direct role in the rapid repopulation of the ground state; it is involved in a S2/S1 crossing. Alternative mechanisms through excited states pisigma* or nNpi* are not competitive in cytosine.
Low lying charmonium states at the physical point
Mohler, Daniel; Kronfeld, Andreas S; Lee, Song-haeng; Levkova, Ludmila; Simone, J N
2014-01-01
We present results for the mass splittings of low-lying charmonium states from a calculation with Wilson clover valence quarks with the Fermilab interpretation on an asqtad sea. We use five lattice spacings and two values of the light sea quark mass to extrapolate our results to the physical point. Sources of systematic uncertainty in our calculation are discussed and we compare our results for the 1S hyperfine splitting, the 1P-1S splitting and the P-wave spin orbit and tensor splittings to experiment.
Radiative Decays of Low-Lying Excited-State Hyperons
Energy Technology Data Exchange (ETDEWEB)
Taylor, Simon [Rice Univ., Houston, TX (United States)
2000-05-01
The quark wave-functions of the lower-lying excited-state hyperons Lambda(1405), Sigma(1385), and Lambda(1520) are not well understood. For example, the Lambda(1405) may not be a regular three-quark state but a $\\bar{K}$N molecule. Several competing models have been proposed, but none have been convincingly eliminated. Measuring radiative decays provides a means of discriminating between the models. The radiative branching of ratios are predicted to be small (~1%), but the radiative widths vary by factors of 2-10 from model to model. The existing experimental data is sparse and inconsistent; moreover, the radiative decay of the Sigma(1385) has never been observed before (except for one event). These lower-lying excited state hypersons were produced in a tagged photon-beam experiment in the CLAS detector at TJNAF in the reaction gamma p → K^{+} Y* for photon energies from threshold to 2.4 GeV. The radiative branching ration for the Sigma^{0}(1385) relative to the Sigma^{0}(1385) → Lambda pi^{0} channel was measured to be 0.021 ± 0.008$+0.004\\atop{-0.007}$, corresponding to a partial width of 640 ± 270$+130\\atop{-220}$ keV.
Zethrenes, Extended p -Quinodimethanes, and Periacenes with a Singlet Biradical Ground State
Sun, Zhe
2014-08-19
ConspectusResearchers have studied polycyclic aromatic hydrocarbons (PAHs) for more than 100 years, and most PAHs in the neutral state reported so far have a closed-shell electronic configuration in the ground state. However, recent studies have revealed that specific types of polycyclic hydrocarbons (PHs) could have a singlet biradical ground state and exhibit unique electronic, optical, and magnetic activities. With the appropriate stabilization, these new compounds could prove useful as molecular materials for organic electronics, nonlinear optics, organic spintronics, organic photovoltaics, and energy storage devices. However, before researchers can use these materials to design new devices, they need better methods to synthesize these molecules and a better understanding of the fundamental relationship between the structure and biradical character of these compounds and their physical properties. Their biradical character makes these compounds difficult to synthesize. These compounds are also challenging to physically characterize and require the use of various experimental techniques and theoretic methods to comprehensively describe their unique properties.In this Account, we will discuss the chemistry and physics of three types of PHs with a significant singlet biradical character, primarily developed in our group. These structures are zethrenes, Z-shaped quinoidal hydrocarbons; hydrocarbons that include a proaromatic extended p-quinodimethane unit; and periacenes, acenes fused in a peri-Arrangement. We used a variety of synthetic methods to prepare these compounds and stabilized them using both thermodynamic and kinetic approaches. We probed their ground-state structures by electronic absorption, NMR, ESR, SQUID, Raman spectroscopy, and X-ray crystallography and also performed density functional theory calculations. We investigated the physical properties of these PHs using various experimental methods such as one-photon absorption, two-photon absorption
Energy Technology Data Exchange (ETDEWEB)
Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel; Hu, Yung-Jin; Lukens, Wayne W.; Bauer, Eric D.; Maron, Laurent; Eisenstein, Odile; Andersen, Richard A.
2009-04-22
Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.
Energy Technology Data Exchange (ETDEWEB)
Bauer, Eric D [Los Alamos National Laboratory; Booth, C H [LBNL; Walter, M D [LBNL; Kazhdan, D [LBNL; Hu, Y - J [LBNL; Lukens, Wayne [LBNL; Maron, Laurent [INSA TOULOUSE; Eisentein, Odile [UNIV MONTPELLIER 2; Anderson, Richard [LBNL
2009-01-01
Partial ytterbium f-orbital occupancy (i.e. intermediate valence) and open-shell singlet Draft 12/formation are established for a variety of bipyridine and diazabutadiene adducts to decamethylytterbocene, (C{sub 5}Me{sub 5}){sub 2}Yb or Cp*{sub 2}Yb. Data used to support this claim includes ytterbium valence measurements using Yb Lm-edge x-ray absorption near-edge structure (XANES) spectroscopy, magnetic susceptibility and Complete Active Space Self-Consistent Field (CASSCF) multi configurational calculations, as well as structural measurements compared to density-functional theory (DFT) calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground state wave function that has both an open-shell singlet f{sup 13} and a closed-shell singlet f{sup 14} component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the presence of intermediate valence and its lack of any significant temperature dependence. These results have implications for understanding chemical bonding not only in organolanthanide complexes, but also for organometallic chemistry in general, as well as understanding magnetic interactions in nanopartic1es and devices.
Singlet-state creation and universal quantum computation in NMR using a genetic algorithm
Manu, V. S.; Kumar, Anil
2012-08-01
The experimental implementation of a quantum algorithm requires the decomposition of unitary operators. Here we treat unitary-operator decomposition as an optimization problem, and use a genetic algorithm—a global-optimization method inspired by nature's evolutionary process—for operator decomposition. We apply this method to NMR quantum information processing, and find a probabilistic way of performing universal quantum computation using global hard pulses. We also demonstrate the efficient creation of the singlet state (a special type of Bell state) directly from thermal equilibrium, using an optimum sequence of pulses.
Singlet state creation and Universal quantum computation in NMR using Genetic Algorithm
Manu, V S
2012-01-01
Experimental implementation of a quantum algorithm requires unitary operator decomposition. Here we treat the unitary operator decomposition as an optimization problem and use Genetic Algorithm, a global optimization method inspired by nature's evolutionary process for operator decomposition. As an application, we apply this to NMR Quantum Information Processing and find a probabilistic way of doing universal quantum computation using global hard pulses. We also demonstrate efficient creation of singlet state (as a special case of Bell state) directly from thermal equilibrium using an optimum sequence of pulses.
Aaron, Jean-Jacques; Diabou Gaye, Mame; Párkányi, Cyril; Cho, Nam Sook; Von Szentpály, László
1987-01-01
The ground-state dipole moments of seven biologically important purines (purine, 6-chloropurine, 6-mercaptopurine, hypoxanthine, theobromine, theophylline and caffeine) were determined at 25°C in acetic acid (all the above compounds with the exception of purine) and in ethyl acetate (purine, theophylline and caffeine). Because of its low solubility, it was not possible to measure the dipole moment of uric acid. The first excited singlet-state dipole moments were obtained on the basis of the Bakhshiev and Chamma—Viallet equations using the variation of the Stokes shift with the solvent dielectric constant-refractive index term. The theoretical dipole moments for all the purines listed above and including uric acid were calculated by combining the use of the PPP (π-LCI-SCF-MO) method for the π-contribution to the overall dipole moment with the σ-contribution obtained as a vector sum of the σbond moments and group moments. The experimental and theoretical values were compared with the data available in the literature for some of the purines under study. For several purines, the calculations were carried out for different tautomeric forms. Excited singlet-state dipole moments are smaller than the ground-state values by 0.8 to 2.2 Debye units for all purines under study with the exception of 6-chloropurine. The effects of the structure upon the ground- and excited-state dipole moments of the purines are discussed.
Probing ground and low-lying excited states for HIO{sub 2} isomers
Energy Technology Data Exchange (ETDEWEB)
Souza, Gabriel L. C. de [Departamento de Química, Universidade Federal de Mato Grosso, Cuiabá, Mato Grosso 78060-900 (Brazil); Instituto de Ciências Exatas e Tecnologia, Universidade Federal do Amazonas, Itacoatiara, Amazonas 69100-000 (Brazil); Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada); Brown, Alex, E-mail: alex.brown@ualberta.ca [Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada)
2014-12-21
We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})
Probing ground and low-lying excited states for HIO2 isomers
de Souza, Gabriel L. C.; Brown, Alex
2014-12-01
We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10-3).
Correlated Pair States Formed by Singlet Fission and Exciton-Exciton Annihilation.
Scholes, Gregory D
2015-12-24
Singlet fission to form a pair of triplet excitations on two neighboring molecules and the reverse process, triplet-triplet annihilation to upconvert excitation, have been extensively studied. Comparatively little work has sought to examine the properties of the intermediate state in both of these processes-the bimolecular pair state. Here, the eigenstates constituting the manifold of 16 bimolecular pair excitations and their relative energies in the weak-coupling regime are reported. The lowest-energy states obtained from the branching diagram method are the triplet pairs with overall singlet spin |X1⟩ ≈ (1)[TT] and quintet spin |Q⟩ ≈ (5)[TT]. It is shown that triplet pair states can be separated by a triplet-triplet energy-transfer mechanism to give a separated, yet entangled triplet pair (1)[T···T]. Independent triplets are produced by decoherence of the separated triplet pair. Recombination of independent triplets by exciton-exciton annihilation to form the correlated triplet pair (i.e., nongeminate recombination) happens with 1/3 of the rate of either triplet migration or recombination of the separated correlated triplet pair (geminate recombination).
Singlet and triplet excited state properties of natural chlorophylls and bacteriochlorophylls
Energy Technology Data Exchange (ETDEWEB)
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.
van Aggelen, Helen; Verstichel, Brecht; Bultinck, Patrick; Van Neck, Dimitri; Ayers, Paul W
2012-01-07
Despite the importance of non-singlet molecules in chemistry, most variational second order density matrix calculations have focused on singlet states. Ensuring that a second order density matrix is derivable from a proper N-electron spin state is a difficult problem because the second order density matrix only describes one- and two-particle interactions. In pursuit of a consistent description of spin in second order density matrix theory, we propose and evaluate two main approaches: we consider constraints derived from a pure spin state and from an ensemble of spin states. This paper makes a comparative assessment of the different approaches by applying them to potential energy surfaces for different spin states of the oxygen and carbon dimer. We observe two major shortcomings of the applied spin constraints: they are not size consistent and they do not reproduce the degeneracy of the different states in a spin multiplet. First of all, the spin constraints are less strong when applied to a dissociated molecule than when they are applied to the dissociation products separately. Although they impose correct spin expectation values on the dissociated molecule, the dissociation products do not have correct spin expectation values. Secondly, both under "pure spin state conditions" and under "ensemble spin state" conditions is the energy a convex function of the spin projection. Potential energy surfaces for different spin projections of the same spin state may give a completely different picture of the molecule's bonding. The maximal spin projection always gives the most strongly constrained energy, but is also significantly more expensive to compute than a spin-averaged ensemble. In the dissociation limit, both the problem of nondegeneracy of equivalent spin projections, size-inconsistency and unphysical dissociation can be corrected by means of subspace energy constraints.
Deceptive Intentions: Can Cues to Deception Be Measured before a Lie Is Even Stated?
National Research Council Canada - National Science Library
Ströfer, S; Noordzij, Matthijs L; Ufkes, E.G; Giebels, Ellen
2015-01-01
.... Both are related to increased sympathetic nervous system (SNS) activity. We hypothesized that SNS activity already rises during intentions to lie and, consequently, cues to deception can be detected before stating an actual lie...
Deceptive Intentions: Can Cues to Deception Be Measured before a Lie Is Even Stated?: e0125237
National Research Council Canada - National Science Library
Sabine Ströfer; Matthijs L Noordzij; Elze G Ufkes; Ellen Giebels
2015-01-01
.... Both are related to increased sympathetic nervous system (SNS) activity. We hypothesized that SNS activity already rises during intentions to lie and, consequently, cues to deception can be detected before stating an actual lie...
The H2+ molecular ion: Low-lying states
Olivares-Pilón, Horacio; Turbiner, Alexander V.
2016-10-01
Matching for a wavefunction the WKB expansion at large distances and Taylor expansion at small distances leads to a compact, few-parametric uniform approximation found in Turbiner and Olivares-Pilon (2011). The ten low-lying eigenstates of H2+ of the quantum numbers (n , m , Λ , ±) with n = m = 0 at Λ = 0 , 1 , 2, with n = 1, m = 0 and n = 0, m = 1 at Λ = 0 of both parities are explored for all interproton distances R. For all these states this approximation provides the relative accuracy ≲ 10-5 (not less than 5 s.d.) locally, for any real coordinate x in eigenfunctions, when for total energy E(R) it gives 10-11 s.d. for R ∈ [ 0 , 50 ] a.u. Corrections to the approximation are evaluated in the specially-designed, convergent perturbation theory. Separation constants are found with not less than 8 s.d. The oscillator strength for the electric dipole transitions E 1 is calculated with not less than 6 s.d. A dramatic dip in the E 1 oscillator strength f 1 sσg - 3 pσu at R ∼Req is observed. The magnetic dipole and electric quadrupole transitions are calculated for the first time with not less than 6 s.d. in oscillator strength. For two lowest states (0 , 0 , 0 , ±) (or, equivalently, 1 sσg and 2 pσu states) the potential curves are checked and confirmed in the Lagrange mesh method within 12 s.d. Based on them the Energy Gap between 1 sσg and 2 pσu potential curves is approximated with modified Pade Re-R [ Pade(8 / 7) ] (R) with not less than 4-5 figures at R ∈ [ 0 , 40 ] a.u. Sum of potential curves E1sσg +E2pσu is approximated by Pade 1 / R [ Pade(5 / 8) ] (R) in R ∈ [ 0 , 40 ] a.u. with not less than 3-4 figures.
Helmich-Paris, Benjamin; Hättig, Christof; van Wüllen, Christoph
2016-04-12
In most organic molecules, phosphorescence has its origin in transitions from triplet exited states to the singlet ground state, which are spin-forbidden in nonrelativistic quantum mechanics. A sufficiently accurate description of phosphorescence lifetimes for molecules that contain only light elements can be achieved by treating the spin-orbit coupling (SOC) with perturbation theory (PT). We present an efficient implementation of this approach for the approximate coupled cluster singles and doubles model CC2 in combination with the resolution-of-the-identity approximation for the electron repulsion integrals. The induced oscillator strengths and phosphorescence lifetimes from SOC-PT are computed within the response theory framework. In contrast to previous work, we employ an explicitly spin-coupled basis for singlet and triplet operators. Thereby, a spin-orbital treatment can be entirely avoided for closed-shell molecules. For compounds containing only light elements, the phosphorescence lifetimes obtained with SOC-PT-CC2 are in good agreement with those of exact two-component (X2C) CC2, whereas the calculations are roughly 12 times faster than with X2C. Phosphorescence lifetimes computed for two thioketones with the SOC-PT-CC2 approach agree very well with reference results from experiment and are similar to those obtained with multireference spin-orbit configuration interaction and with X2C-CC2. An application to phosphorescent emitters for metal-free organic light-emitting diodes (OLEDs) with almost 60 atoms and more than 1800 basis functions demonstrates how the approach extends the applicability of coupled cluster methods for studying phosphorescence. The results indicate that other decay channels like vibrational relaxation may become important in such systems if lifetimes are large.
Low-lying electronic states of M(3)O(9)(-) and M(3)O(9)(2-) (M = Mo, W).
Li, Shenggang; Dixon, David A
2007-11-01
Multiple low-lying electronic states of M(3)O(9)(-) and M(3)O(9)(2-) (M = Mo, W) arise from the occupation of the near-degenerate low-lying virtual orbitals in the neutral clusters. We used density functional theory (DFT) and coupled cluster theory (CCSD(T)) with correlation consistent basis sets to study the structures and energetics of the electronic states of these anions. The adiabatic and vertical electron detachment energies (ADEs and VDEs) of the anionic clusters were calculated with 27 exchange-correlation functionals including one local spin density approximation functional, 13 generalized gradient approximation (GGA) functionals, and 13 hybrid GGA functionals, as well as the CCSD(T) method. For M(3)O(9)(-), CCSD(T) and nearly all of the DFT exchange-correlation functionals studied predict the (2)A(1) state arising from the Jahn-Teller distortion due to singly occupying the degenerate e' orbital to be lower in energy than the (2)A(1)' state arising from singly occupying the nondegenerate a(1)' orbital. For W(3)O(9)(-), the (2)A(1) state was predicted to have essentially the same energy as the (2)A(1)' state at the CCSD(T) level with core-valence correlation corrections included and to be higher in energy or essentially isoenergetic with most DFT methods. The calculated VDEs from the CCSD(T) method are in reasonable agreement with the experimental values for both electronic states if estimates for the corrections due to basis set incompleteness are included. For M(3)O(9)(2-), the singlet state arising from doubly occupying the nondegenerate a(1)' orbital was predicted to be the most stable state for both M = Mo and W. However, whereas M(3)O(9)(2-) was predicted to be less stable than M(3)O(9)(-), W(3)O(9)(2-) was predicted to be more stable than W(3)O(9)(-).
Radiative lifetime of the metastable excited singlet A^1Σ^+ state of (CaNa)^+
Makarov, Oleg P.; Côté, R.; Michels, H.; Smith, W. W.
2002-05-01
New experiments were proposed recently to investigate the regime of cold atomic and molecular ion-atom collision processes in a special hybrid neutral-atom--ion trap under high vacuum conditions. The collisional cooling of laser pre-cooled Ca^+ ions by ultracold Na atoms is being studied. Modeling this process requires knowledge of the radiative lifetime of the excited metastable singlet A^1Σ^+ state of the (CaNa)^+ molecular system. We present calculations for the oscillator strength values of free-bound transitions between the A^1Σ^+ and ground X^1Σ^+ states of the molecular system. The calculations were carried out using Complete Active Set Self-Consistent Field and Möller-Plesset second order perturbation theory (CASSCF/MP2) with an extended Gaussian basis, 6-311+G(3df). These states asymptotically go to the excited (Ca^+ +Na(3s)) and ground (Na^+ +Ca) limits of the ion-atom quasimolecular system, respectively. The matrix elements between low-energy free excited states and individual vibrational levels of the ground state are calculated, and the resulting matrix elements are summed to obtain the integrated collisional radiative lifetime. We are investigating the competition between collisional cooling and heating from radiative charge transfer. Work is supported in part by NSF grant PHY-9988215.
Grebenshchikov, Sergy Yu
2013-01-01
The absorption spectrum of CO$_2$ in the wavelength range 120\\,nm --- 160\\,nm is analyzed by means of quantum mechanical calculations performed using vibronically coupled PESs of five singlet valence electronic states and the coordinate dependent transition dipole moment vectors. The thermally averaged spectrum, calculated for T=190\\,K via Boltzmann averaging of optical transitions from many initial rotational states, accurtely reproduces the experimental spectral envelope, consisting of a low and a high energy band, the positions of the absorption maxima, their FWHMs, peak intensities, and frequencies of diffuse structures in each band. Contributions of the vibronic interactions due to Renner-Teller coupling, conical intersections, and the Herzberg-Teller effect are isolated and the calculated bands are assigned in terms of adiabatic electronic states. Finally, diffuse structures in the calculated bands are vibronically assigned using wave functions of the underlying resonance states. It is demonstrated that...
Tagawa, S.; Washio, M.; Tabata, Y.; Kobayashi, H.
Transient absorption spectra of the solute anion, cation and triplet state and the solute fluorescence in the pulse radiolysis of 0.1 mole 1 -1 biphenyl in cyclohexane were observed on a nanosecond timescale longer than 1 ns after a 20 ps pulse. The formation of the solute excited singlet state is mainly due to the geminate ion recombination reaction even in the high concentrated solutions. The decay of the solute ions obeys the reciprocal square root dependence on time longer than 10 ns from the end of a 10 ps pulse. The slope of this reciprocal square root plots agrees with the literature value on a longer timescale obtained by microwave absorption. The yield of free ions obtained from the intercept of the slope agrees also with the literature values obtained by the field clearing method. Ratio of the formation rate of the solute excited triplet state to the decay rate of the solute anion changes in a time range between 5 and 20 ns. It is very well correlated with a theoretical calculation of spin correlation decay of the germinate ion pairs by Brocklehurst, although the formation of the solute triplet state was observed even on a timescale shorter than 5 ns from the end of a 20 ps pulse, where loss of spin correlation is negligibly small.
Toward Designed Singlet Fission: Electronic States and Photophysics of 1,3-Diphenylisobenzofuran
Energy Technology Data Exchange (ETDEWEB)
Schwerin, A.F.; Miller, J.; Johnson, J.C.; Smith, M.B.; Sreearunothai, P.; Popovic, D.; Cerny, J.; Havlas, Z.; Paci, I.; Akdag, A.; MacLeod, M.K.; Chen, X.; David, D.E.; Ratner, M.A.; Nozik, A.J.; Mich, J.
2009-12-21
Single crystal molecular structure and solution photophysical properties are reported for 1,3-diphenylisobenzofuran (1), of interest as a model compound in studies of singlet fission. For the ground state of 1 and of its radical cation (1{sup +{sm_bullet}}) and anion (1{sup -{sm_bullet}}), we report the UV-visible absorption spectra, and for neutral 1, also the magnetic circular dichroism (MCD) and the decomposition of the absorption spectrum into purely polarized components, deduced from fluorescence polarization. These results were used to identify a series of singlet excited states. For the first excited singlet and triplet states of 1, the transient visible absorption spectra, S{sub 1} {yields} S{sub x} and sensitized T{sub 1} {yields} T{sub x}, and single exponential lifetimes, {tau}{sub F} = {approx} 5.3 ns and {tau}{sub T} = {approx}200 {mu}s, are reported. The spectra and lifetimes of S{sub 1} {yields} S{sub 0} fluorescence and sensitized T{sub 1} {yields} T{sub x} absorption of 1 were obtained in a series of solvents, as was the fluorescence quantum yield, {Phi}{sub F} = 0.95-0.99. No phosphorescence has been detected. The first triplet excitation energy of solid 1 (11,400 cm{sup -1}) was obtained by electron energy loss spectroscopy, in agreement with previously reported solution values. The fluorescence excitation spectrum suggests an onset of a nonradiative channel at {approx} 37,000 cm{sup -1}. Excitation energies and relative transition intensities are in agreement with those of ab initio (CC2) calculations after an empirical 3000 cm{sup -1} adjustment of the initial state energy to correct differentially for a better quality description of the initial relative to the terminal state of an absorption transition. The interpretation of the MCD spectrum used the semiempirical PPP method, whose results for the S{sub 0} {yields} S{sub x} spectrum require no empirical adjustment and are otherwise nearly identical with the CC2 results in all respects
Tempelaar, Roel; Reichman, David R.
2017-05-01
Recent time-resolved spectroscopic experiments have indicated that vibronic coupling plays a vital role in facilitating the process of singlet fission. In this work, which forms the first article of a series, we set out to unravel the mechanisms underlying singlet fission through a vibronic exciton theory. We formulate a model in which both electronic and vibrational degrees of freedom are treated microscopically and non-perturbatively. Using pentacene as a prototypical material for singlet fission, we subject our theory to comparison with measurements on polarization-resolved absorption of single crystals, and employ our model to characterize the excited states underlying the absorption band. Special attention is given to the convergence of photophysical observables with respect to the basis size employed, through which we determine the optimal basis for more expensive calculations to be presented in subsequent work. We furthermore evaluate the energetic separation between the optically prepared singlet excited state and the correlated triplet pair state, as well as provide a real-space characterization of the latter, both of which are of key importance in the discussion of fission dynamics. We discuss our results in the context of recent experimental studies.
Microscopic Description of Low-Lying Isovector Quadrupole States in /sup 56/Fe
Energy Technology Data Exchange (ETDEWEB)
Nikolaeva, R.; Stoyanov, C.; Vdovin, A.I.
1989-01-01
Microscopic calculations of energies, structure and transition probabilities of low-lying 2/sup +/ states in /sup 56/Fe have been performed in the framework of the quasi-particle phonon nuclear model. The interaction of the phonons appears to play an important role in determination of the isotopic character of low-lying quadrupole states.
Noncollisional excitation of low-lying states in gaseous nebulae
Rubin, Robert H.
1986-01-01
Consideration is given to the effects of processes other than electron collisional excitation on the energy level populations of species of C, N, and O. It is found that dielectronic as well as direct-radiative recombination may contribute significantly and in some cases be the major input to populating the low-lying metastable levels. It is concluded that the most pronounced changes occur when there is a large effective recombination coefficient to a level and when T(e) is low. The most dramatic change among the forbidden lines occurs for the O II forbidden lines.
On the low-lying states of TiN
Bauschlicher, C. W., Jr.
1983-01-01
A series of CAS SCF and multi-reference CI calculations are used to describe the lowest states of TiN. The bonding in all states is described as a triple bond involving the Ti 3d orbitals. The system has some ionic character as seen from both population analysis and dipole moment. The origins of the excited states are discussed.
Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku
2016-04-18
One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface.
Bozkaya, Uğur; Turney, Justin M; Yamaguchi, Yukio; Schaefer, Henry F
2012-04-28
The lowest-lying electronic singlet and triplet potential energy surfaces (PES) for the HNO-NOH system have been investigated employing high level ab initio quantum chemical methods. The reaction energies and barriers have been predicted for two isomerization and four dissociation reactions. Total energies are extrapolated to the complete basis set limit applying focal point analyses. Anharmonic zero-point vibrational energies, diagonal Born-Oppenheimer corrections, relativistic effects, and core correlation corrections are also taken into account. On the singlet PES, the (1)HNO → (1)NOH endothermicity including all corrections is predicted to be 42.23 ± 0.2 kcal mol(-1). For the barrierless decomposition of (1)HNO to H + NO, the dissociation energy is estimated to be 47.48 ± 0.2 kcal mol(-1). For (1)NOH → H + NO, the reaction endothermicity and barrier are 5.25 ± 0.2 and 7.88 ± 0.2 kcal mol(-1). On the triplet PES the reaction energy and barrier including all corrections are predicted to be 7.73 ± 0.2 and 39.31 ± 0.2 kcal mol(-1) for the isomerization reaction (3)HNO → (3)NOH. For the triplet dissociation reaction (to H + NO) the corresponding results are 29.03 ± 0.2 and 32.41 ± 0.2 kcal mol(-1). Analogous results are 21.30 ± 0.2 and 33.67 ± 0.2 kcal mol(-1) for the dissociation reaction of (3)NOH (to H + NO). Unimolecular rate constants for the isomerization and dissociation reactions were obtained utilizing kinetic modeling methods. The tunneling and kinetic isotope effects are also investigated for these reactions. The adiabatic singlet-triplet energy splittings are predicted to be 18.45 ± 0.2 and 16.05 ± 0.2 kcal mol(-1) for HNO and NOH, respectively. Kinetic analyses based on solution of simultaneous first-order ordinary-differential rate equations demonstrate that the singlet NOH molecule will be difficult to prepare at room temperature, while the triplet NOH molecule is viable with respect to isomerization and dissociation reactions up to
Iuchi, Satoru
2012-02-14
A simple model electronic Hamiltonian to describe the potential energy surfaces of several low-lying d-d states of the [Fe(bpy)(3)](2+) complex is developed for use in molecular dynamics (MD) simulation studies. On the basis of a method proposed previously for first-row transition metal ions in aqueous solution, the model Hamiltonian is constructed using density functional theory calculations for the lowest singlet and quintet states. MD simulations are then carried out for the two spin states in aqueous solution in order to examine the performance of the model Hamiltonian. The simulation results indicate that the present model electronic Hamiltonian reasonably describes the potential energy surfaces of the two spin states of the aqueous [Fe(bpy)(3)](2+) system, while retaining sufficient simplicity for application in simulation studies on excited state dynamics.
DMRG-SCF study of the singlet, triplet, and quintet states of oxo-Mn(Salen)
Wouters, Sebastian; Van Der Voort, Pascal; Van Speybroeck, Veronique; Van Neck, Dimitri
2014-01-01
We use CheMPS2, our free open-source spin-adapted implementation of the density matrix renormalization group (DMRG) [Wouters et al., Comput. Phys. Commun. 185, 1501 (2014)], to study the lowest singlet, triplet, and quintet states of the oxo-Mn(Salen) complex. We describe how an initial approximate DMRG calculation in a large active space around the Fermi level can be used to obtain a good set of starting orbitals for subsequent complete-active-space or DMRG self-consistent field (CASSCF or DMRG-SCF) calculations. This procedure mitigates the need for a localization procedure, followed by a manual selection of the active space. Per multiplicity, the same active space of 28 electrons in 22 orbitals (28e, 22o) is obtained with the 6-31G*, cc-pVDZ, and ANO-RCC-VDZP basis sets (the latter with DKH2 scalar relativistic corrections). Our calculations provide new insight into the electronic structure of the quintet.
Initial singlet and triplet spin state contributions to -> ppπ0
Thörngren Engblom, P.; Meyer, H. O.; Balewski, J. T.; Daehnick, W. W.; Doskow, J.; Haeberli, W.; Lorentz, B.; Pancella, P. V.; Pollock, R. E.; von Przewoski, B.; Rathmann, F.; Rinckel, T.; Saha, Swapan K.; Schwartz, B.; Wellinghausen, A.; Wise, T.
2000-01-01
The PINTEX2http://www.iucf.indiana.edu/~pintex/refid="fn2">2 facility at the IUCF Cooler ring, dedicated to the study of spin dependence in nucleon-nucleon interactions, has been used to measure polarization observables of the reaction -> ppπ0 at beam energies between 325 and 400 MeV. The stored, polarized proton beam had spin projections both in the longitudinal and the transverse directions with respect to the beam momentum. We report here on the measurements of the relative transverse and longitudinal spin-dependent cross sections3Defined as ΔσT(L) = [σ(⇕) + σ(⇕)] - [σ(⇈ + σ(⇊)] where the arrows denote parallel and antiparallel beam/target spin combinations, either transversely (T) or longitudinally (L) polarized.refid="fn3">3, ΔσT/σtot and ΔσL/σtot, and how from these observables the initial spin singlet and triplet cross sections are obtained. Considering angular momentum states less than or equal to one, the contribution of the Ps partial waves to the cross section can be extracted.
Deceptive Intentions: Can Cues to Deception Be Measured before a Lie Is Even Stated?
Ströfer, Sabine; Noordzij, Matthijs L.; Ufkes, Elze G.; Giebels, Ellen
2015-01-01
Can deceitful intentions be discriminated from truthful ones? Previous work consistently demonstrated that deceiving others is accompanied by nervousness/stress and cognitive load. Both are related to increased sympathetic nervous system (SNS) activity. We hypothesized that SNS activity already rises during intentions to lie and, consequently, cues to deception can be detected before stating an actual lie. In two experiments, controlling for prospective memory, we monitored SNS activity during lying, truth telling, and truth telling with the aim of lying at a later instance. Electrodermal activity (EDA) was used as an indicator of SNS. EDA was highest during lying, and compared to the truth condition, EDA was also raised during the intention to deceive. Moreover, the switch from truth telling toward lying in the intention condition evoked higher EDA than switching toward non-deception related tasks in the lie or truth condition. These results provide first empirical evidence that increased SNS activity related to deception can be monitored before a lie is stated. This implies that cues to deception are already present during the mere intention to lie. PMID:26018573
Theoretical Study of the Low-Lying States of MgN+2
Maitre, Philippe; Bauschlicher, Charles W., Jr.; Gross, Anthony R. (Technical Monitor)
1994-01-01
The structure and binding energies of the low-lying states of MgN2+ have been computed at the multireference configuration interaction level of theory. The effect of Mg inner-shell correlation have been included using the core-polarization potential method. The charge-quadrupole interaction results in a linear 2Sigma+ ground state as expected. The excited states can arise from either the interaction of the 2-P state of Mg+ with N2 or from charge transfer states with Mg(sup 2+)N2- bonding character. The lowest lying excited state, 2-B2, is mixture of these two mechanisms, which results in a C2v, geometry with Mg atoms sitting at the N2 bond midpoint. The small barrier in the bending potential exists between this state and the 2-II State which is the lowest lying linear excited state.
Low-lying charmed and charmed-strange baryon states
Energy Technology Data Exchange (ETDEWEB)
Chen, Bing [Anyang Normal University, Department of Physics, Anyang (China); Institute of Modern Physics of CAS and Lanzhou University, Research Center for Hadron and CSR Physics, Lanzhou (China); Wei, Ke-Wei [Anyang Normal University, Department of Physics, Anyang (China); Liu, Xiang [Lanzhou University, School of Physical Science and Technology, Lanzhou (China); Institute of Modern Physics of CAS and Lanzhou University, Research Center for Hadron and CSR Physics, Lanzhou (China); Matsuki, Takayuki [Tokyo Kasei University, Tokyo (Japan); Nishina Center, RIKEN, Theoretical Research Division, Saitama (Japan)
2017-03-15
In this work, we systematically study the mass spectra and strong decays of 1P and 2S charmed and charmed-strange baryons in the framework of non-relativistic constituent quark models. With the light quark cluster-heavy quark picture, the masses are simply calculated by a potential model. The strong decays are studied by the Eichten-Hill-Quigg decay formula. Masses and decay properties of the well-established 1S and 1P states can be reproduced by our method. Σ{sub c}(2800){sup 0,+,++} can be assigned as a Σ{sub c2}(3/2{sup -}) or Σ{sub c2}(5/2{sup -}) state. We prefer to interpret the signal Σ{sub c}(2850){sup 0} as a 2S(1/2{sup +}) state although at present we cannot thoroughly exclude the possibility that this is the same state as Σ{sub c}(2800){sup 0}. Λ{sub c}(2765){sup +} or Σ{sub c}(2765){sup +} could be explained as the Λ{sub c}{sup +}(2S) state or Σ{sup +}{sub c1}(1/2{sup -}) state, respectively. We propose to measure the branching ratio of B(Σ{sub c}(2455)π)/B(Σ{sub c}(2520)π) in the future, which may disentangle the puzzle of this state. Our results support Ξ{sub c}(2980){sup 0,+} as the first radial excited state of Ξ{sub c}(2470){sup 0,+} with J{sup P} = 1/2{sup +}. The assignment of Ξ{sub c}(2930){sup 0} is analogous to Σ{sub c}(2800){sup 0,+,++}, i.e., a Ξ{sup '}{sub c2}(3/2{sup -}) or Ξ{sup '}{sub c2}(5/2{sup -}) state. In addition, we predict some typical ratios among partial decay widths, which are valuable for experimental search for these missing charmed and charmed-strange baryons. (orig.)
Low-lying ($K^{} = 0^{+}$) states of gadolinium isotopes
Indian Academy of Sciences (India)
Harun Reşit Yazar
2013-10-01
The sd-interacting boson approximation (sd-IBA) and the df-interacting boson approximation (df-IBA) can be related to each other and the states of the interacting boson approximation model can be identified with the fully symmetric states in the sdf interacting boson approximation model. A systematic study of the sdf-IBA model showed that the constructed Hamiltonian can successfully describe the strong octupole correlations in the deformed nuclei. We showed that the interacting boson approximation may account for many of these $K^{} = 0^{+}$ states. It was found that the calculated energy spectra of the gadolinium isotopes agree quite well with the experimental data. The observed (2) values were also calculated and compared with the experimental data.
Electron delocalization and aromaticity in low-lying excited states of archetypal organic compounds.
Feixas, Ferran; Vandenbussche, Jelle; Bultinck, Patrick; Matito, Eduard; Solà, Miquel
2011-12-14
Aromaticity is a property usually linked to the ground state of stable molecules. Although it is well-known that certain excited states are unquestionably aromatic, the aromaticity of excited states remains rather unexplored. To move one step forward in the comprehension of aromaticity in excited states, in this work we analyze the electron delocalization and aromaticity of a series of low-lying excited states of cyclobutadiene, benzene, and cyclooctatetraene with different multiplicities at the CASSCF level by means of electron delocalization measures. While our results are in agreement with Baird's rule for the aromaticity of the lowest-lying triplet excited state in annulenes having 4nπ-electrons, they do not support Soncini and Fowler's generalization of Baird's rule pointing out that the lowest-lying quintet state of benzene and septet state of cyclooctatetraene are not aromatic.
Isomerism of low-lying states in {sup 86}Y
Energy Technology Data Exchange (ETDEWEB)
Rusu, C. [Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest (Romania); University of Texas at Dallas, School of Natural Sciences and Mathematics, Richardson, TX (United States); Bucurescu, D.; Marginean, N.; Ionescu-Bujor, M.; Iordachescu, A.; Cata-Danil, G.; Cata-Danil, I.; Deleanu, D.; Filipescu, D.; Ghita, D.; Glodariu, T.; Ivascu, M.; Mihai, C.; Marginean, R.; Pascu, S.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N.V. [Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest (Romania)
2010-04-15
Low-energy isomeric states of {sup 86}Y were populated in the reaction {sup 73}Ge + {sup 16}O at 57MeV and were investigated by means of delayed n {gamma} and {gamma} {gamma} coincidences. A half-life of 70(7)ns was measured for the 5{sup -} state at 208keV, yielding an exceptionally small B(M1) value of 2.0(7) x 10{sup -5} W.u. and a B(E2) value of 0.34({sup +24} {sub -13}) W.u. For the other three known isomeric states at 218, 243, and 302keV, the half-lives extracted from the present experimental data are in very good agreement with previous measurements. Given the newly observed isomeric character of the 5{sup -} 208keV state, the re-analysis of earlier experimental data on the 302keV isomer led to a new spin-parity assignment, 6{sup +}, for this state. In addition, this re-evaluation provided two g -factors, -0.083(3) and +0.63(2), for the 208 and 302keV states, respectively. The results are discussed in terms of spherical-shell model calculations performed with a truncated space of configurations built on the f{sub 5/2}, p{sub 3/2}, p{sub 1/2}, and g{sub 9/2} valence orbitals. Effective spin, orbital, and ''tensor'' g -factors were determined empirically for protons and neutrons in the considered configuration space. (orig.)
The low-lying electronic states of LiC
Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)
1995-01-01
The spectroscopic constants for the doublet and quartet states of LiC below about 30,000/cm are determined using an internally contracted multireference configuration-interaction approach in conjunction with a [6s 5p 3d 2f] atomic natural orbital basis sets. All of the strongly bound states, X(sup 4)(SIGMA)(sup -),(1)(sup 2)(DELTA), (1)(sup 2)(SIGMA)(sup +), and (2)(sup 2) II, very ionic in character. The only bound-bound quartet transition in this energy range is (2)(sup 4)SIGMA(sup -) and Franck-Condon factors, Einstein A values, and lifetimes are reported for this transition.
Theoretical characterization of low-lying electronic states of FCO
Francisco, Joseph S.; Goldstein, Avery N.; Robb, Michael A.; Williams, Ian H.
1992-03-01
The electronic and vibrational spectra of the fluoroformyl radical FCO are discussed in the light of ab initio (CASSCF(5 in 4)/6-31+G* and UMP2/6-311G*) calculated adiabatic and vertical transition energies, and vibrational frequencies, for the X 2A', A 2A″, B 2A', and C 2A″ states. Results for the formyl radical HCO are also presented for comparison.
Grebenshchikov, Sergy Yu.
2013-06-01
The absorption spectrum of CO2 in the wavelength range 120-160 nm is analyzed by means of quantum mechanical calculations performed using vibronically coupled potential energy surfaces of five singlet valence electronic states and the coordinate dependent transition dipole moment vectors. The thermally averaged spectrum, calculated for T = 190 K via Boltzmann averaging of optical transitions from many initial rotational states, accurately reproduces the experimental spectral envelope, consisting of a low and a high energy band, the positions of the absorption maxima, their FWHMs, peak intensities, and frequencies of diffuse structures in each band. Contributions of the vibronic interactions due to Renner-Teller coupling, conical intersections, and the Herzberg-Teller effect are isolated and the calculated bands are assigned in terms of adiabatic electronic states. Finally, diffuse structures in the calculated bands are vibronically assigned using wave functions of the underlying resonance states. It is demonstrated that the main progressions in the high energy band correspond to consecutive excitations of the pseudorotational motion along the closed loop of the CI seam, and progressions differ in the number of nodes along the radial mode perpendicular to the closed seam. Irregularity of the diffuse peaks in the low energy band is interpreted as a manifestation of the carbene-type "cyclic" OCO minimum.
Grebenshchikov, Sergy Yu.
2013-01-01
The global potential energy surfaces of the first six singlet electronic states of CO$_2$, 1---3$^1/!A'$ and 1---3$^1/!A"$ are constructed using high level ab initio calculations. In linear molecule, they correspond to $\\tilde{X}^1\\Sigma_g^+$, $1^1\\Delta_u$, $1^1\\Sigma_u^-$, and $1^1\\Pi_g$. The calculations accurately reproduce the known benchmarks for all states and establish missing benchmarks for future calculations. The calculated states strongly interact at avoided crossings and true int...
Global Correlations for Low-Lying Collective 2+ States
Qin, Z. Z.; Lei, Y.; Pittel, S.; Bijker, R.
2017-07-01
By using the triaxial rotor model and the anharmonic vibrator model with phonon mixing, we derive a global correlation between the quadrupole moments of the two lowest 2+ states in collective nuclei that had previously been observed in experimental data across the periodic table. We then derive other electromagnetic properties for these two models of nuclear structure and compare them globally with experimental data. We find that both models are able to robustly describe the experimental data across the region of nuclei for which the models are applicable, including a large number that they have in common. We then show that there seems to exists a robust orthogonal transformation between these two models for realistic nuclear systems, suggesting that these two seemingly diverse descriptions of quadrupole collective phenomena seem to act in a similar model space and may therefore have a common origin.
Singlet Molecular Oxygen on Ice: Rates of Formation and Steady State Concentrations
Bower, J. P.; Anastasio, C.
2007-12-01
Singlet molecular oxygen (1O2*), the first electronically excited state of molecular oxygen, reacts rapidly with certain types of environmental pollutants such as furans, phenols, and polycyclic aromatic hydrocarbons (PAHs). Its formation requires the absorption of light by a chromophore (a.k.a. sensitizer), which subsequently transfers energy to ground state molecular oxygen. In the environment, 1O2* chemistry has been studied primarily in the aqueous phase, such as in surface waters or cloud and fog drops. In this work, we expand our current understanding by investigating the rate of formation (Rf) and steady state concentration ([1O2*]) of 1O2* on ice. To investigate 1O2* kinetics, we use a chemical probe technique in which photoformed 1O2* reacts with furfuryl alcohol (FFA). To generate 1O2*, we illuminated frozen samples containing a sensitizer (Rose Bengal, RB) at 549 nm. The concentration of total solutes in each sample was controlled using sodium sulfate (Na2SO4). Following illumination, the decay of FFA was measured using high performance liquid chromatography (HPLC). Ice tests were conducted at 253, 263, and 268 K. Liquid tests for comparison were conducted at 278 K. Results showed dramatically faster (~104) FFA decay on ice than in liquid samples prepared from the same solutions, in agreement with the calculated solute concentration factor in the quasi-liquid layer (QLL) on ice compared to bulk solution. Varying the concentration of RB resulted in similar changes in both Rf and [1O2*], with magnitudes of change close to those expected. Changing temperature and total solutes, both of which control the volume of the QLL on ice, revealed two model regimes: FFA as a major (1) or minor (2) sink of 1O2*. Experimental results from the former regime show good agreement with expected values for both Rf and [1O2*]. Experiments in the later regime are currently in progress. We will also discuss the potential implications of 1O2* to the chemistry of naturally
Spectroscopy of high-lying states in actinide nuclei
Energy Technology Data Exchange (ETDEWEB)
Ahmad, I.; Back, B.B.; Betts, R.R. [and others
1995-08-01
In the course of studying positron-electron production during the collisions of uranium beams and tantalum targets, a careful measurement of the emitted gamma radiation was made using large Ge detectors. Many new high energy gamma rays were found, associated both with U-like and Ta-like fragments. To determine the origin of these gamma rays, a dedicated set of improved gamma-ray studies were carried out. The studies used four large (> 55%) Ge detectors mounted in the APEX chamber. States in {sup 238}U and {sup 232}Th were Coulomb excited using a {sup 208}Pb beam of 5.8 MeV/u. Heavy ions were detected in the large-area APEX multiwire proportional counters. The extensive beam monitoring of the APEX setup allowed precise normalization and accurate cross-section determinations. The Doppler shifts from upstream and downstream detectors permitted a precise confirmation of the incident beam energy to less than 0.05 MeV/A. A spectrum of gamma rays, corrected assuming emission from {sup 238}U.
Energies of low-lying excited states of linear polyenes.
Christensen, Ronald L; Galinato, Mary Grace I; Chu, Emily F; Howard, Jason N; Broene, Richard D; Frank, Harry A
2008-12-11
Room temperature absorption and emission spectra of the all-trans isomers of decatetraene, dodecapentaene, tetradecahexaene, and hexadecaheptaene have been obtained in a series of nonpolar solvents. The resolved vibronic features in the optical spectra of these model systems allow the accurate determination of S(0) (1(1)A(g)(-)) --> S(2) (1(1)B(u)(+)) and S(1) (2(1)A(g)(-)) --> S(0) (1(1)A(g)(-)) electronic origins as a function of solvent polarizability. These data can be extrapolated to predict the transition energies in the absence of solvent perturbations. The effects of the terminal methyl substituents on the transition energies also can be estimated. Franck-Condon maxima in the absorption and emission spectra were used to estimate differences between S(0) (1(1)A(g)(-)) --> S(1) (2(1)A(g)(-)) and S(0) (1(1)A(g)(-)) --> S(2) (1(1)B(u)(+)) electronic origins and "vertical" transition energies. Experimental estimates of the vertical transition energies of unsubstituted, all-trans polyenes in vacuum as a function of conjugation length are compared with long-standing multireference configuration interaction (MRCI) treatments and with more recent ab initio calculations of the energies of the 2(1)A(g)(-) (S(1)) and 1(1)B(u)(+) (S(2)) states.
Grebenshchikov, Sergy Yu.
2013-06-01
The global potential energy surfaces of the first six singlet electronic states of CO2, 1—31A', and 1—31A″ are constructed using high level ab initio calculations. In linear molecule, they correspond to tilde{X}^1Σ _g^+, 11Δu, 1^1Σ _u^-, and 11Πg. The calculations accurately reproduce the known benchmarks for all states and establish missing benchmarks for future calculations. The calculated states strongly interact at avoided crossings and true intersections, both conical and glancing. Near degeneracies can be found for each pair of six states and many intersections involve more than two states. In particular, a fivefold intersection dominates the Franck-Condon zone for the ultraviolet excitation from the ground electronic state. The seam of this intersection traces out a closed loop. All states are diabatized, and a diabatic 5 × 5 potential matrix is constructed, which can be used in quantum mechanical calculations of the absorption spectrum of the five excited singlet valence states.
Institute of Scientific and Technical Information of China (English)
冯东太; 丁世良; 王美山
2003-01-01
The highly excited vibrational states of asymmetric linear tetratomic molecules are studied in the framework of Lie algebra. By using symmetric group U1(4) U2(4) U3(4), we construct the Hamiltonian that includes not only Casimir operators but also Majorana operators M12,M13 and M23, which are useful for getting potential energy surface and force constants in Lie algebra method. By Lie algebra treatment, we obtain the eigenvalues of the Hamiltonian, and make the concrete calculation for molecule C2HF.
Coincidence spectroscopy of high-lying Rydberg states produced in strong laser fields
Larimian, Seyedreza; Erattupuzha, Sonia; Lemell, Christoph; Yoshida, Shuhei; Nagele, Stefan; Maurer, Raffael; Baltuška, Andrius; Burgdörfer, Joachim; Kitzler, Markus; Xie, Xinhua
2016-09-01
We demonstrate the detection of high-lying Rydberg states produced in strong laser fields with coincidence spectroscopy. Electron emission after the interaction of strong laser pulses with atoms and molecules is measured together with the parent ions in coincidence measurements. These electrons originate from high-lying Rydberg states with quantum numbers from n ˜20 up to n ≲120 formed by frustrated field ionization. Ionization rates are retrieved from the measured ionization signal of these Rydberg states. Simulations show that both tunneling ionization by a weak dc field and photoionization by blackbody radiation contribute to delayed electron emission on the nano- to microsecond scale. Furthermore, the dependence of the Rydberg-state production on the ellipticity of the driving laser field indicates that such high-lying Rydberg states are populated through electron recapture. The present experiment provides detailed quantitative information on Rydberg production in strong-field interaction.
DEFF Research Database (Denmark)
Reynisson, J.; Wilbrandt, R.; Brinck, V.
2002-01-01
of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown...
Multicomponent Group-Related Coherent States for Lie Group Chain G K
Institute of Scientific and Technical Information of China (English)
HE Hui-Yong; LI Guang-Hua; LI Jiang-Fan
2001-01-01
The multicomponent group-related coherent states for the Lie group chain G K are introduced. Their coupling coefficients are presented. The relations between these coupling coefficients and those (in the usual sense) of the irreducible representation bases labelled by G K are obtained. The generalized Racah's factorization lemma about the coupling coefficients of such coherent states is given. As an example, the multicomponent group-related coherent states for the Lie group chain Sp(4) D SO(3)1 S0(3)2 are found. The uncertainty relation and the squeezing property are discussed.``
EXCITATION OF LOW-LYING STATES IN ND-144 BY MEANS OF (E,E') SCATTERING
PERRINO, R; BLASI, N; DELEO, R; HARAKEH, MN; DEJAGER, CW; MICHELETTI, S; MIEREMET, J; PIGNANELLI, M; PONOMAREV, VY; SANDOR, RKJ; DEVRIES, H
1993-01-01
The low-lying states of Nd-144 have been investigated up to an excitation energy of 3.1 MeV by means of high-resolution inelastic electron scattering. Transition charge densities have been extracted for natural-parity states. The experimental data have been compared with the predictions of the quasi
Low-lying Photoexcited States of a One-Dimensional Ionic Extended Hubbard Model
Yokoi, Kota; Maeshima, Nobuya; Hino, Ken-ichi
2017-10-01
We investigate the properties of low-lying photoexcited states of a one-dimensional (1D) ionic extended Hubbard model at half-filling. Numerical analysis by using the full and Lanczos diagonalization methods shows that, in the ionic phase, there exist low-lying photoexcited states below the charge transfer gap. As a result of comparison with numerical data for the 1D antiferromagnetic (AF) Heisenberg model, it was found that, for a small alternating potential Δ, these low-lying photoexcited states are spin excitations, which is consistent with a previous analytical study [Katsura et al., Phys. Rev. Lett. 103, 177402 (2009)]. As Δ increases, the spectral intensity of the 1D ionic extended Hubbard model rapidly deviates from that of the 1D AF Heisenberg model and it is clarified that this deviation is due to the neutral-ionic domain wall, an elementary excitation near the neutral-ionic transition point.
Ozone absorption spectroscopy in search of low-lying electronic states
Anderson, S. M.; Mauersberger, K.
1995-01-01
A spectrometer capable of detecting ozone absorption features 9 orders of magnitude weaker than the Hartley band has been employed to investigate the molecule's near-infrared absorption spectrum. At this sensitivity a wealth of information on the low-lying electronically excited states often believed to play a role in atmospheric chemistry is available in the form of vibrational and rotational structure. We have analyzed these spectra using a combination of digital filtering and isotope substitution and find evidence for three electronically excited states below 1.5 eV. The lowest of these states is metastable, bound by approximately 0.1 eV and probably the (3)A2 rather than the (3)B2 state. Its adiabatic electronic energy is 1.24 +/- 0.01 eV, slightly above the dissociation energy of the ground state. Two higher states, at 1.29 +/- 0.03 and 1.48 +/- 0.03 eV are identified as the (3)B2 and the (3)B1, respectively. Combined with other recent theoretical and experimental data on the low-lying electronic states of ozone, these results imply that these are, in fact, the lowest three excited states; that is, there are no electronically excited states of ozone lying below the energy of O(3P) + O2((3)Sigma(-), v = 0). Some of the implications for atmospheric chemistry are considered.
RDDS lifetime measurements of low-lying superdeformed states in {sup 194}Hg
Energy Technology Data Exchange (ETDEWEB)
Kuehn, R.; Dewald, A.; Kruecken, R. [Universitaet Koeln (Germany)] [and others
1996-12-31
The lifetimes of three low-lying states in the superdeformed (SD) yrast band of {sup 194}Hg were measured by the recoil-distance Doppler-shift method. The deduced transition quadrupole moments, Q{sub t}, equal those extracted from a DSAM measurement for the high-lying states of the band corroborate the assumption that the decay out of SD bands does not strongly affect the structure of the corresponding states. By a simple mixing-model the decay can be described assuming a very small admixture of normal-deformed (ND) states to the decaying SD states. The deduced ND mixing amplitudes for the yrast SD bands in {sup 192,194}Hg and {sup 194}Pb are presented along with average transition quadrupole moments for the lower parts of the excited SD bands.
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.
Iterative solutions for low lying excited states of a class of Schr(o)dinger equation
Institute of Scientific and Technical Information of China (English)
R.Friedberga; T.D.Lee; Zhao Wei-Qin
2006-01-01
The convergent iterative procedure for solving the groundstate Schr(o)dinger equation is extended to derive the excitation energy and the wavefunction of the low-lying excited states. The method is applied to the one-dimensional quartic potential problem. The results show that the iterative solution converges rapidly when the coupling g is not too small.
Iterative Solutions for Low Lying Excited States of a Class of Schroedinger Equation
Friedberg, R; Zhao, W Q
2006-01-01
The convergent iterative procedure for solving the groundstate Schroedinger equation is extended to derive the excitation energy and the wave function of the low-lying excited states. The method is applied to the one-dimensional quartic potential problem. The results show that the iterative solution converges rapidly when the coupling $g$ is not too small.
Coherent states, quantum gravity, and the Born- Oppenheimer approximation. II. Compact Lie groups
Stottmeister, Alexander; Thiemann, Thomas
2016-07-01
In this article, the second of three, we discuss and develop the basis of a Weyl quantisation for compact Lie groups aiming at loop quantum gravity-type models. This Weyl quantisation may serve as the main mathematical tool to implement the program of space adiabatic perturbation theory in such models. As we already argued in our first article, space adiabatic perturbation theory offers an ideal framework to overcome the obstacles that hinder the direct implementation of the conventional Born-Oppenheimer approach in the canonical formulation of loop quantum gravity. Additionally, we conjecture the existence of a new form of the Segal-Bargmann-Hall "coherent state" transform for compact Lie groups G, which we prove for G = U(1)n and support by numerical evidence for G = SU(2). The reason for conjoining this conjecture with the main topic of this article originates in the observation that the coherent state transform can be used as a basic building block of a coherent state quantisation (Berezin quantisation) for compact Lie groups G. But, as Weyl and Berezin quantisation for ℝ2d are intimately related by heat kernel evolution, it is natural to ask whether a similar connection exists for compact Lie groups as well. Moreover, since the formulation of space adiabatic perturbation theory requires a (deformation) quantisation as minimal input, we analyse the question to what extent the coherent state quantisation, defined by the Segal-Bargmann-Hall transform, can serve as basis of the former.
Short-range correlations in low-lying nuclear excited states
Mokhtar, S R; Lallena, A M; Mokhtar, Sherif R.; Co', Giampaolo; Lallena, Antonio M.
2000-01-01
The electromagnetic transitions to various low-lying excited states of 16O, 48Ca and 208Pb are calculated within a model which considers the short-range correlations. In general the effects of the correlations are small and do not explain the required quenching to describe the data.
THE ACQM THEORETICAL CALCULATION OF LOW—LYING EXCITED STATES FOR HeH
Institute of Scientific and Technical Information of China (English)
Q.Q.GOU; Z.Y.Huang; 等
1990-01-01
The Low-lying excited states of HeH have been calculated by arrangement channel quantum mechanics(ACQM),The calculated potential curves,equilibrium geometry,Rc.dissociation energy Dc.harmonic vibration frequency ω0 and quadratic force coustant F2 are comparable with Ci calculations.
Cluster Decay of the High-lying excited states in $^{14}$C
Tian, Z Y; Li, Z H; Lin, C J; Li, Q T; Ge, Y C; Lou, J L; Jiang, W; Li, J; Yang, Z H; Feng, J; Li, P J; Chen, J; Liu, Q; Zang, H L; Yang, B; Zhang, Y; Chen, Z Q; Liu, Y; Sun, X H; Ma, J; Jia, H M; Xu, X X; Yang, L; Ma, N R; Sun, L J
2016-01-01
A cluster-transfer experiment of $^9\\rm{Be}(^9\\rm{Be},^{14}\\rm{C}\\rightarrow\\alpha+^{10}\\rm{Be})\\alpha$ at an incident energy of 45 MeV was carried out in order to investigate the molecular structure in high-lying resonant states in $^{14}$C. This reaction is of extremely large $Q$-value, making it an excellent case to select the reaction mechanism and the final states in outgoing nuclei. The high-lying resonances in $^{14}$C are reconstructed for three sets of well discriminated final states in $^{10}$Be. The results confirm the previous decay measurements with clearly improved decay-channel selections and show also a new state at 23.5(1) MeV. The resonant states at 22.4(3) and 24.0(3) MeV decay primarily into the typical molecular states at about 6 MeV in $^{10}$Be, indicating a well developed cluster structure in these high-lying states in $^{14}$C. Further measurements of more states of this kind are suggested.
Cluster decay of the high-lying excited states in 14C
Tian, Z. Y.; Ye, Y. L.; Li, Z. H.; Lin, C. J.; Li, Q. T.; Ge, Y. C.; Lou, J. L.; Jiang, W.; Li, J.; Yang, Z. H.; Feng, J.; Li, P. J.; Chen, J.; Liu, Q.; Zang, H. L.; Yang, B.; Zhang, Y.; Chen, Z. Q.; Liu, Y.; Sun, X. H.; Ma, J.; Jia, H. M.; Xu, X. X.; Yang, L.; Ma, N. R.; Sun, L. J.
2016-11-01
A cluster-transfer experiment of 9Be(9Be,14C → α+10Be)α at an incident energy of 45 MeV was carried out in order to investigate the molecular structure in high-lying resonant states in 14C. This reaction is of extremely large Q-value, making it an excellent case to select the reaction mechanism and the final states in outgoing nuclei. The high-lying resonances in 14C are reconstructed for three sets of well discriminated final states in 10Be. The results confirm the previous decay measurements with clearly improved decay-channel selections and also show a new state at 23.5(1) MeV. The resonant states at 22.4(3) and 24.0(3) MeV decay primarily into the typical molecular states at about 6 MeV in 10Be, indicating a well developed cluster structure in these high-lying states in 14C. Further measurements of more states of this kind are suggested. Supported by the 973 Program of China (2013 CB834402) and National Natural Science Foundation of China (11275011, 11535004)
A theoretical study of the low-lying states of Ti2 and Zr2
Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.; Rosi, Marzio
1991-01-01
The low-lying states of Ti2 and the valence isoelectronic Zr2 are examined theoretically by means of a multireference configuration-interaction (MRCI) method. MRCI calculations demonstrate that two of the Zr2 states are very low-lying and that the resulting vertical excitation is consistent with the optical spectrum of Zr2. The ground state is predicted for Ti2 on the basis of valence correlation with the MRCI method and the average coupled-pair functional technique. Calculations of the inner-shell correlation effects are estimated and found to lower the 3Delta g state to a ground state, and another to a very low-lying state. The ground state of Ti2 is assigned to 3Delta g since it is lower than the other state at all levels of correlation and is derived from the same atomic asymptote. This conclusion is supported by the lack of an electron-spin resonance signal but contradicts the absence of subcomponents on the Raman spectral lines.
Meyling, J.H.; Werf, R.P. van der
1974-01-01
High resolution absorption and laser-induced emission spectra of the lowest B3u(nπ*) singlet state of s-tetrazine-h2 and -d2 in a benzene crystal at 1.8 K are presented and discussed. The absorption spectrum with origin at 17231 cm-1 (h2) is dominated by a progression in ν6a and a Herzberg-Teller or
Obukhov, A. E.
2016-12-01
In this work we demonstrate the physical foundations of the spectroscopy of the grounds states: E- and X-ray, (RR) Raman scattering the NMR 1H and 13C and IR-, EPR- absorption and the singlets and triplets electronic excited states in the multinuclear hydrocarbons in chemmotology. The parameters of UV-absorption, RR-Raman scattering of light, the fluorescence and the phosphorescence and day-lasers at the pumping laser and lamp, OLEDs and OTETs- are measurements. The spectral-energy properties are briefly studied. The quantum-chemical LCAO-MO SCF expanded-CI PPP/S and INDO/S methods in the electronic and spatial structure hidrocarbons are considered.
Classification of lying states for the humanoid robot SJTU-HR1
Institute of Scientific and Technical Information of China (English)
无
2009-01-01
The humanoid robot SJTU-HR1’s concept is introduced and its characteristics tree is given.The basic states for SJTU-HR1 are proposed,including lying,sitting,standing and handstanding,abstracted from the daily exercises of human beings.The GF(generalized function) set theory is exploited to achieve the kinematic characteristics of the interested EEs(end-effectors) of SJTU-HR1 for the lying states.Finally,the results show that the large amounts of states can be described using the abbreviations in a systematic manner.Although we have focused on the application of the GF set theory to humanoid robots,particularly the SJTU-HR1,this methodology can also be applied to quadruped robots and hexapedal robots,especially when the desired tasks are complex.
Classification of lying states for the humanoid robot SJTU-HR1
Institute of Scientific and Technical Information of China (English)
YANG JiaLun; GAO Feng; JIN ZhenLin; SHI LiFeng
2009-01-01
The humanoid robot SJTU-HRI's concept is introduced and its characteristics tree is given. The basic states for SJTU-HR1 are proposed, including lying, sitting, standing and handstsnding, abstracted from the daily exercises of human beings. The GF (generalized function) set theory is exploited to achieve the kinematic characteristics of the interested EEs (end-effectors) of SJTU-HR1 for the lying states.Finally, the results show that the large amounts of states can be described using the abbreviations in a systematic manner. Although we have focused on the application of the GF set theory to humanoid robots, particularly the SJTU-HR1, this methodology can also be applied to quadruped robots and hexapedal robots, especially when the desired tasks are complex.
Computed potential surfaces for six low-lying states of Ni3
Walch, Stephen P.
1987-01-01
Selected portions of the potential surfaces for six low lying states of Ni3 are the subject of the present SCF/CCI calculations using the effective core potentials developed by Hay and Wadt (1985); the four states are studied for near-equilateral triangle geometries are within 0.04 eV of each other. Two states are studied for linear geometries, of which the first is 0.16 eV higher than the corresponding near-equilateral triangle state and the second is estimated to be nearly degenerate with the near-equilateral triangle structures.
A model of low-lying states in strongly interacting electroweak symmetry-breaking sector
Han, T; Hung, P Q; Han, Tao; Huang, Zheng; Hung, P Q
1994-01-01
We present a tumbling scenario for the generation of low-lying states in a strongly interacting electroweak sector. The dynamical calculation using the N/D method indicates that when the interactions among the Goldstone and Higgs bosons become sufficiently strong, an axial vector state A_1 [I^G(J^P)=1^-(1^+)] emerges. The coexistence of vector states V [1^+(1^-)] and \\omega_H [0^-(1^-)] is suggested by requiring the proper Regge behavior of the forward scattering. These states may lead to distinctive experimental signatures at the future colliders.
Hannesdottir, H.; Gudmundsson, J. T.
2017-05-01
We apply particle-in-cell simulations with Monte Carlo collisions to study the influence of the singlet metastable states on the ion energy distribution in single and dual frequency capacitively coupled oxygen discharges. For this purpose, the one-dimensional object-oriented particle-in-cell Monte Carlo collision code oopd1 is used, in which the discharge model includes the following nine species: electrons, the neutrals O(3P) and O{{}2}≤ft({{\\text{X}}3} Σ g-\\right. ), the negative ions O-, the positive ions O+ and O2+ , and the metastables O(1D), O{{}2}≤ft({{\\text{a}}1}{{ Δ }g}\\right) and O2(b{{}1} Σ g+ ). Earlier, we have explored the effects of adding the species O{{}2}≤ft({{\\text{a}}1}{{ Δ }g}\\right. ) and O2(b{{}1} Σ g+ ), and an energy-dependent secondary electron emission yield for oxygen ions and neutrals, to the discharge model. We found that including the two molecular singlet metastable states decreases the ohmic heating and the effective electron temperature in the bulk region (the electronegative core). Here we explore how these metastable states influence dual frequency discharges consisting of a fundamental frequency and the lowest even harmonics. Including or excluding the detachment reactions of the metastables O{{}2}≤ft({{\\text{a}}1}{{ Δ }g}\\right. ) and O2(b{{}1} Σ g+ ) can shift the peak electron temperature from the grounded to the powered electrode or vice versa, depending on the phase difference of the two applied frequencies. These metastable states can furthermore significantly influence the peak of the ion energy distribution for O2+ -ions bombarding the powered electrode, and hence the average ion energy upon bombardment of the electrode, and lower the ion flux.
Does a proton "bubble" structure exist in the low-lying states of 34Si?
Yao, J M; Li, Z P
2013-01-01
The possible existence of a "bubble" structure in the proton density of $^{34}$Si has recently attracted a lot of research interest. To examine the existence of the "bubble" structure in low-lying states, we establish a relativistic version of configuration mixing of both particle number and angular momentum projected quadrupole deformed mean-field states and apply this state-of-the-art beyond relativistic mean-field method to study the density distribution of the low-lying states in $^{34}$Si. An excellent agreement with the data of low-spin spectrum and electric multipole transition strengths is achieved without introducing any parameters. We find that the central depression in the proton density is quenched by dynamic quadrupole shape fluctuation, but not as significantly as what has been found in a beyond non-relativistic mean-field study. Our results suggest that the existence of proton "bubble" structure in the low-lying excited $0^+_2$ and $2^+_1$ states is very unlikely.
Almeida, D. E.; Fernandes, R. M.; Miranda, E.
2017-07-01
The close interplay between superconductivity and antiferromagnetism in several quantum materials can lead to the appearance of an unusual thermodynamic state in which both orders coexist microscopically, despite their competing nature. A hallmark of this coexistence state is the emergence of a spin-triplet superconducting gap component, called a π triplet, which is spatially modulated by the antiferromagnetic wave vector, reminiscent of a pair density wave. In this paper, we investigate the impact of these π -triplet degrees of freedom on the phase diagram of a system with competing antiferromagnetic and superconducting orders. Although we focus on a microscopic two-band model that has been widely employed in studies of iron pnictides, most of our results follow from a Ginzburg-Landau analysis, and as such should be applicable to other systems of interest, such as cuprates and heavy fermion materials. The Ginzburg-Landau functional reveals not only that the π -triplet gap amplitude couples trilinearly with the singlet gap amplitude and the staggered magnetization magnitude but also that the π -triplet d -vector couples linearly with the magnetization direction. While in the mean-field level this coupling forces the d -vector to align parallel or antiparallel to the magnetization, in the fluctuation regime it promotes two additional collective modes—a Goldstone mode related to the precession of the d -vector around the magnetization and a massive mode, related to the relative angle between the two vectors, which is nearly degenerate with a Leggett-like mode associated with the phase difference between the singlet and triplet gaps. We also investigate the impact of magnetic fluctuations on the superconducting-antiferromagnetic phase diagram, showing that due to their coupling with the π -triplet order parameter the coexistence region is enhanced. This effect stems from the fact that the π -triplet degrees of freedom promote an effective attraction between
Kumari, Rekha; Varghese, Anitha; George, Louis
2017-01-01
Absorption and fluorescence studies on novel Schiff bases (E)-4-(4-(4-nitro benzylideneamino)benzyl)oxazolidin-2-one (NBOA) and (E)-4-(4-(4-chlorobenzylidene amino)benzyl)oxazolidin-2-one (CBOA) were recorded in a series of twelve solvents upon increasing polarity at room temperature. Large Stokes shift indicates bathochromic fluorescence band for both the molecules. The photoluminescence properties of Schiff bases containing electron withdrawing and donating substituents were analyzed. Intramolecular charge transfer behavior can be studied based on the influence of different substituents in Schiff bases. Changes in position and intensity of absorption and fluorescence spectra are responsible for the stabilization of singlet excited-states of Schiff base molecules with different substituents, in polar solvents. This is attributed to the Intramolecular charge transfer (ICT) mechanism. In case of electron donating (-Cl) substituent, ICT contributes largely to positive solvatochromism when compared to electron withdrawing (-NO2) substituent. Ground-state and singlet excited-state dipole moments of NBOA and CBOA were calculated experimentally using solvent polarity function approaches given by Lippert-Mataga, Bakhshiev, Kawskii-Chamma-Viallet and Reichardt. Due to considerable π- electron density redistribution, singlet excited-state dipole moment was found to be greater than ground-state dipole moment. Ground-state dipole moment value which was determined by quantum chemical method was used to estimate excited-state dipole moment using solvatochromic correlations. Kamlet-Abboud-Taft and Catalan multiple linear regression approaches were used to study non-specific solute-solvent interaction and hydrogen bonding interactions in detail. Optimized geometry and HOMO-LUMO energies of NBOA and CBOA have been determined by DFT and TD-DFT/PCM (B3LYP/6-311G (d, p)). Mulliken charges and molecular electrostatic potential have also been evaluated from DFT calculations.
Search for Singlet Fission Chromophores
Energy Technology Data Exchange (ETDEWEB)
Havlas, Z.; Akdag, A.; Smith, M. B.; Dron, P.; Johnson, J. C.; Nozik, A. J.; Michl, J.
2012-01-01
Singlet fission, in which a singlet excited chromophore shares its energy with a ground-state neighbor and both end up in their triplet states, is of potential interest for solar cells. Only a handful of compounds, mostly alternant hydrocarbons, are known to perform efficiently. In view of the large number of conditions that a successful candidate for a practical cell has to meet, it appears desirable to extend the present list of high performers to additional classes of compounds. We have (i) identified design rules for new singlet fission chromophores and for their coupling to covalent dimers, (ii) synthesized them, and (iii) evaluated their performance as neat solids or covalent dimers.
Grebenshchikov, Sergy Yu
2013-01-01
The global potential energy surfaces of the first six singlet electronic states of CO$_2$, 1---3$^1/!A'$ and 1---3$^1/!A"$ are constructed using high level ab initio calculations. In linear molecule, they correspond to $\\tilde{X}^1\\Sigma_g^+$, $1^1\\Delta_u$, $1^1\\Sigma_u^-$, and $1^1\\Pi_g$. The calculations accurately reproduce the known benchmarks for all states and establish missing benchmarks for future calculations. The calculated states strongly interact at avoided crossings and true intersections, both conical and glancing. Near degeneracies can be found for each pair of six states and many intersections involve more than two states. In particular, a fivefold intersection dominates the Franck-Condon zone for the ultraviolet excitation from the ground electronic state. The seam of this intersection traces out a closed loop. All states are diabatized, and a diabatic $5\\times 5$ potential matrix is constructed, which can be used in quantum mechanical calculations of the absorption spectrum of the five exci...
Transition from vibrational to rotational character in low-lying states of hypernuclei
Mei, H.; Hagino, K.; Yao, J. M.; Motoba, T.
2017-07-01
In order to clarify the nature of hypernuclear low-lying states, we carry out a comprehensive study of the structure of Λ 145-155Sm hypernuclei, which exhibit a transition from vibrational to rotational character as the neutron number increases. To this end, we employ a microscopic particle-core coupling scheme based on a covariant density functional theory. We find that the positive-parity ground-state band in the hypernuclei shares a similar structure to that of the corresponding core nucleus. That is, regardless of whether the core nucleus is spherical or deformed, each hypernuclear state is dominated by the single configuration of the Λ particle in the s1 /2 state (Λ s1 /2 ) coupled to one core state of the ground band. In contrast, the low-lying negative-parity states mainly consist of Λ p1 /2 and Λ p3 /2 configurations coupled to plural nuclear core states. We show that, while the mixing amplitude between these configurations is negligibly small in spherical and weakly deformed nuclei, it strongly increases as the core nucleus undergoes a transition to a well deformed shape, which is consistent with the Nilsson wave functions. We demonstrate that the structure of these negative-parity states with spin I can be well understood based on a naive L S coupling scheme, with total orbital angular momentum L =[I ⊗1 ] and spin angular momentum S =1 /2 .
A new analytical potential energy surface for the singlet state of He{sub 2}H{sup +}
Energy Technology Data Exchange (ETDEWEB)
Liang Jingjuan; Zhang Qinggang [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); Yang Chuanlu [School of Physics, Ludong University, Yantai 264011 (China); Wang Lizhi [College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China); School of Physics, Ludong University, Yantai 264011 (China)
2012-03-07
The analytic potential energy surface (APES) for the exchange reaction of HeH{sup +} (X{sup 1}{Sigma}{sup +}) + He at the lowest singlet state 1{sup 1}A{sup /} has been built. The APES is expressed as Aguado-Paniagua function based on the many-body expansion. Using the adaptive non-linear least-squares algorithm, the APES is fitted from 15 682 ab initio energy points calculated with the multireference configuration interaction calculation with a large d-aug-cc-pV5Z basis set. To testify the new APES, we calculate the integral cross sections for He + H{sup +}He (v= 0, 1, 2, j= 0) {yields} HeH{sup +}+ He by means of quasi-classical trajectory and compare them with the previous result in literature.
Shell model description of low-lying states in Po and Rn isotopes
Higashiyama, Koji; Yoshinaga, Naotaka
2014-03-01
Nuclear structure of the Po and Rn isotopes is theoretically studied in terms of the spherical shell model with the monopole- and quadrupole-pairing plus quadrupole-quadrupole effective interaction. The experimental energy levels of low-lying states are well reproduced. The shell model results are examined in detail in a pair-truncated shell model. The analysis reveals the alignment of two protons in the 0h9/2 orbital at spin 8.
Shell model description of low-lying states in Po and Rn isotopes
Directory of Open Access Journals (Sweden)
Higashiyama Koji
2014-03-01
Full Text Available Nuclear structure of the Po and Rn isotopes is theoretically studied in terms of the spherical shell model with the monopole- and quadrupole-pairing plus quadrupole-quadrupole effective interaction. The experimental energy levels of low-lying states are well reproduced. The shell model results are examined in detail in a pair-truncated shell model. The analysis reveals the alignment of two protons in the 0h9/2 orbital at spin 8.
Observations and theoretical analysis of highly excited singlet and triplet states of cadmium
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.
The Low-Lying States of AlCu and AlAg
Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry
1994-01-01
The singlet and triplet states of AlCu and AlAg below about 32 000/cm are studied using the internally contracted multireference configuration-interaction method. A more elaborate study of the X(sup 1)Sum(sup +) ground state of AlCu is undertaken using extended Gaussian basis sets, including the effect of inner-shell correlation and including a perturbational estimate of relativistic effects. Our best estimate of the spectroscopic constants (r(sub 0), DeltaG(sub 1/2), and D(sub 0)) for the X(sup 1)Sum(sup+) state with the experimental values in parentheses are: 4.416(4.420) a(sub 0), 295 (294) /cm, and 2.318 (2.315) eV. The calculations definitively assign the upper state in the observed transition at 14 892/cm to the lowest (sup 1)Prod state. The calculated spectroscopic constants and radiative lifetime for the (sup 1)Prod state are in good agreement with experiment. The calculations support the tentative assignments of Behm et al. for three band systems observed in the visible region between 25 000 and 28 000 / cm. However, the computed spectroscopic constants are in very poor agreement with those deduced from an analysis of the spectra. Analogous theoretical results for AlAg suggest that the (2)(sup 3)Prod, (3)(sup 3)Prod, and (3)(sup 1)Sum(sup +) states account for the bands observed, but not assigned, by Duncan and co-workers.
Wang, Huan; Zhu, Chaoyuan; Yu, Jian-Guo; Lin, Sheng Hsien
2009-12-31
Anharmonic effects of the absorption and fluorescence spectra of pyridine molecule are studied and analyzed for the two-low lying singlet excited states S(1)((1)B(1)) and S(2)((1)B(2)). The complete active space self-consistent field (CASSCF) method is utilized to compute equilibrium geometries and all 27 vibrational normal-mode frequencies for the ground state and the two excited states. The present calculations show that the frequency differences between the ground and two excited states are small for the ten totally symmetric vibrational modes so that the displaced oscillator approximation can be used for spectrum simulations. The Franck-Condon factors within harmonic approximation basically grasp the main features of molecular spectra, but simulated 0-0 transition energy position and spectrum band shapes are not satisfactorily good for S(1)((1)B(1)) absorption and fluorescence spectra in comparison with experiment observation. As the first-order anharmonic correction added to Franck-Condon factors, both spectrum positions and band shapes can be simultaneously improved for both absorption and fluorescence spectra. It is concluded that the present anharmonic correction produces a significant dynamic shifts for spectrum positions and improves spectrum band shapes as well. The detailed structures of absorption spectrum of S(2)((1)B(2)) state observed from experiment can be also reproduced with anharmonic Franck-Condon simulation, and these were not shown in the harmonic Franck-Condon simulation with either distorted or Duschinsky effects in the literature.
Ground and Low-Lying Collective States of Rotating Three-Boson System
Imran, Mohd.; Ahsan, M. A. H.
2016-04-01
The ground and low-lying collective states of a rotating system of N = 3 bosons harmonically confined in quasi-two-dimension and interacting via repulsive finite-range Gaussian potential is studied in weakly to moderately interacting regime. The N-body Hamiltonian matrix is diagonalized in subspaces of quantized total angular momenta 0 ≥ L ≥ 4N to obtain the ground and low-lying eigenstates. Our numerical results show that breathing modes with N-body eigenenergy spacing of 2ħω⊥, known to exist in strictly 2D system with zero-range (δ-function) interaction potential, may as well exist in quasi-2D system with finite-range Gaussian interaction potential. To gain an insight into the many-body states, the von Neumann entropy is calculated as a measure of quantum correlation and the conditional probability distribution is analyzed for the internal structure of the eigenstates. In the rapidly rotating regime the ground state in angular momentum subspaces L = (q/2)N (N - 1) with q = 2, 4 is found to exhibit the anticorrelation structure suggesting that it may variationally be described by a Bose-Laughlin like state. We further observe that the first breathing mode exhibits features similar to the Bose-Laughlin state in having eigenenergy, von Neumann entropy and internal structure independent of interaction for the three-boson system considered here. On the contrary, for eigenstates lying between the Bose-Laughlin like ground state and the first breathing mode, values of eigenenergy, von Neumann entropy and internal structure are found to vary with interaction.
Doppler-shift attenuation method lifetime measurements of low-lying states in {sup 111}In
Energy Technology Data Exchange (ETDEWEB)
Bucurescu, D.; Cata-Danil, I.; Ilas, G.; Ivascu, M.; Marginean, N.; Stroe, L.; Ur, C.A. [Institute of Atomic Physics, P.O. Box MG-6, Bucharest 76900 (Romania)
1996-11-01
The lifetimes of nine low-lying excited states in {sup 111}In have been measured with the Doppler-shift attenuation method in the {sup 111}Cd({ital p},{ital n}{gamma}) reaction. A comparison of experimental quantities with predictions based on the interacting boson-fermion model unravels the states due to the coupling of a {ital g}{sub 9/2} proton hole to the quadrupole vibrations of the core. {copyright} {ital 1996 The American Physical Society.}
DEFF Research Database (Denmark)
Rosenberg, Martin; Ottosson, Henrik; Kilså, Kristine
2010-01-01
Aromaticity has importance for proton and hydride affinities in the singlet ground state (S(0)) of annulenyl anions and cations so that, e.g., cyclopentadiene is an acidic hydrocarbon. For the lowest pipi* excited triplet state (T(1)), Baird's rule concludes that annulenes with 4n pi-electrons ar......Aromaticity has importance for proton and hydride affinities in the singlet ground state (S(0)) of annulenyl anions and cations so that, e.g., cyclopentadiene is an acidic hydrocarbon. For the lowest pipi* excited triplet state (T(1)), Baird's rule concludes that annulenes with 4n pi......-electrons are aromatic and those with 4n+2 pi-electrons are antiaromatic, opposite to Huckel's rule for aromaticity in S(0). Our hypothesis is now that the relative magnitudes of proton and hydride affinities of annulenyl anions and cations reverts systematically as one goes from S(0) to T(1) as a result of the opposite...... electron counting rules for aromaticity in the two states. Using quantum chemical calculations at the G3(MP2)//(U)B3LYP/6-311+G(d,p) level we have examined the validity of this hypothesis for eight proton and eight hydride addition reactions of anions and cations, respectively, of annulenyl...
Spectroscopy of low-lying states in neutron-deficient astatine and francium nuclei
Energy Technology Data Exchange (ETDEWEB)
Jakobsson, U., E-mail: ulrjak@kth.se; Cederwall, B. [KTH, The Division of Nuclear Physics, AlbaNova University Center, SE-10691 Stockholm (Sweden); Uusitalo, J.; Auranen, K.; Badran, H.; Cox, D. M.; Grahn, T.; Greenlees, P. T.; Julin, R.; Juutinen, S.; Herzáň, A.; Konki, J.; Leino, M.; Mallaburn, M.; Pakarinen, J.; Papadakis, P.; Partanen, J.; Rahkila, P.; Sandzelius, M.; Sarén, J. [University of Jyvaskyla, Department of Physics, P.O. Box 35, FI-40014 University of Jyvaskyla (Finland); and others
2015-10-15
Low-lying states in neutron-deficient astatine and francium nuclei have been studied by means of in-beam and delayed spectroscopy. The 13/2{sup +} state has been observed in francium nuclei with a similar down-sloping trend as in neighbouring astatine and bismuth isotopes, as a function of decreasing neutron number. A systematic trend can also now be seen for the 1/2{sup +} state both in astatine and francium nuclei, where the level energy decreases steeply as a function of neutron number when moving further away from the neutron shell closure. This trend is very similar between astatine nuclei and their francium isotones. Moreover, shape coexistence has been observed between the 13/2{sup +} state and the spherical 9/2{sup −} ground state in {sup 203}Fr and {sup 205}Fr.
Shukla, M K; Leszczynski, Jerzy
2005-09-15
An ab-initio computational study was performed to investigate the effect of explicit hydration on the ground and lowest singlet PiPi* excited-state geometry and on the selected stretching vibrational frequencies corresponding to the different NH sites of the guanine acting as hydrogen-bond donors. The studied systems consisted of guanine interacting with one, three, five, six, and seven water molecules. Ground-state geometries were optimized at the HF level, while excited-state geometries were optimized at the CIS level. The 6-311G(d,p) basis set was used in all calculations. The nature of potential energy surfaces was ascertained via the harmonic vibrational frequency analysis; all structures were found minima at the respective potential energy surfaces. The changes in the geometry and the stretching vibrational frequencies of hydrogen-bond-donating sites of the guanine in the ground and excited state consequent to the hydration are discussed. It was found that the first solvation shell of the guanine can accommodate up to six water molecules. The addition of the another water molecule distorts the hydrogen-bonding network by displacing other neighboring water molecules away from the guanine plane.
Decay properties of low-lying collective states in sup 1 sup 3 sup 2 Ba
Gade, A; Meise, H; Gelberg, A; Brentano, P V
2002-01-01
The decay properties of low-lying collective states in sup 1 sup 3 sup 2 Ba were studied by means of gamma spectroscopy following the beta-decay of the 2 sup - ground state (T sub 1 sub / sub 2 =4.8 h) and a 6 sup - isomer (T sub 1 sub / sub 2 =24.3 min) of sup 1 sup 3 sup 2 La. The lanthanum nuclei were produced at the Cologne FN TANDEM accelerator using the reaction sup 1 sup 2 sup 2 Sn( sup 1 sup 4 N, 4n) sup 1 sup 3 sup 2 La. The gamma gamma coincidences and singles spectra were measured with the OSIRIS-cube spectrometer. Beside ground and quasi-gamma band many other low-lying states were observed. The gamma gamma angular correlations were analyzed to assign spins to the excited states, and to determine the multipolarities of the depopulating the gamma transitions. We also confirmed the expected dominant E2 character of transitions in the quasi-gamma band and from the quasi-gamma to the ground band but with a certain deviation: the decay 6 sup + sub 2->6 sup + sub 1 shows an unexpected large M1 fraction. ...
On the low-lying states of MgO. II
Bauschlicher, C. W., Jr.; Lengsfield, B. H., III; Silver, D. M.; Yarkony, D. R.
1981-01-01
Using a double zeta plus polarization basis set of Slater orbitals, full valence MCSCF (FVMCSCF) calculations were performed for the low-lying states of MgO. For each state the FVMCSCF calculations were used to identify the important configurations which are then used in the MCSCF calculation and subsequently as references in a single and double excitation CI calculation. This approach is found to treat all states equivalently, with the maximum error in the computed transition energies and equilibrium bond lengths of 800/cm and approximately 0.03 A, respectively. The b 3 Sigma + state which has yet to be characterized experimentally is predicted to have a transition energy of approximately 8300/cm and a bond length of 1.79 A. A spectroscopic analysis of the potential curves indicates that their shapes are in quite reasonable agreement with the range of experimental results.
On the low-lying states of MgO. II
Bauschlicher, C. W., Jr.; Lengsfield, B. H., III; Silver, D. M.; Yarkony, D. R.
1981-01-01
Using a double zeta plus polarization basis set of Slater orbitals, full valence MCSCF (FVMCSCF) calculations were performed for the low-lying states of MgO. For each state the FVMCSCF calculations were used to identify the important configurations which are then used in the MCSCF calculation and subsequently as references in a single and double excitation CI calculation. This approach is found to treat all states equivalently, with the maximum error in the computed transition energies and equilibrium bond lengths of 800/cm and approximately 0.03 A, respectively. The b 3 Sigma + state which has yet to be characterized experimentally is predicted to have a transition energy of approximately 8300/cm and a bond length of 1.79 A. A spectroscopic analysis of the potential curves indicates that their shapes are in quite reasonable agreement with the range of experimental results.
Iuchi, Satoru; Koga, Nobuaki
2014-01-14
With the aim of exploring excited state dynamics, a model electronic Hamiltonian for several low-lying d-d states of [Fe(bpy)3](2+) complex [S. Iuchi, J. Chem. Phys. 136, 064519 (2012)] is refined using density-functional theory calculations of singlet, triplet, and quintet states as benchmarks. Spin-orbit coupling elements are also evaluated within the framework of the model Hamiltonian. The accuracy of the developed model Hamiltonian is determined by examining potential energies and spin-orbit couplings at surface crossing regions between different spin states. Insights into the potential energy surfaces around surface crossing regions are also provided through molecular dynamics simulations. The results demonstrate that the constructed model Hamiltonian can be used for studies on the d-d excited state dynamics of [Fe(bpy)3](2+).
Forbidden Transition Probabilities of Astrophysical Interest among Low-lying States of V III
Indian Academy of Sciences (India)
Andrei Irimia
2007-06-01
Electric and magnetic multipole transitions among low-lying states of doubly ionized vanadium were computed using the multi-configuration Hartree–Fock (MCHF) method with Breit–Pauli (BP) corrections to a non-relativistic Hamiltonian. Energy levels were determined up to and including 32(1)4 b 27/2 and computed energies were found to be in good agreement with experiment and other theories. In addition to Einstein coefficients for some E2 and M1 transitions, lifetime data and selected weighted oscillator strengths are also reported.
Directory of Open Access Journals (Sweden)
Mohammad Shahzad
2016-05-01
Full Text Available This study deals with the control of chaotic dynamics of tumor cells, healthy host cells, and effector immune cells in a chaotic Three Dimensional Cancer Model (TDCM by State Space Exact Linearization (SSEL technique based on Lie algebra. A non-linear feedback control law is designed which induces a coordinate transformation thereby changing the original chaotic TDCM system into a controlled one linear system. Numerical simulation has been carried using Mathematica that witness the robustness of the technique implemented on the chosen chaotic system.
A New Approach to Solve the Low-lying States of the Schroedinger Equation
Lee Tsung Dao
2005-01-01
We review a new iterative procedure to solve the low-lying states of the Schroedinger equation, done in collaboration with Richard Friedberg. For the groundstate energy, the $n^{th}$ order iterative energy is bounded by a finite limit, independent of $n$; thereby it avoids some of the inherent difficulties faced by the usual perturbative series expansions. For a fairly large class of problems, this new procedure can be proved to give convergent iterative solutions. These convergent solutions include the long standing difficult problem of a quartic potential with either symmetric or asymmetric minima.
Proton core polarization in low-lying states of 86Sr
Connelly, J. P.; Milliman, T. E.; Heisenberg, J. H.; Hersman, F. W.; Wise, J. E., III; Papanicolas, C. N.
1990-11-01
Electron-scattering cross sections, measured between 0.4 and 3.1 fm-1, have been unfolded to obtain charge transition densities for the low-lying 2+, 4+, 6+, and 8+ states in 86Sr. A comparison is made to analogous levels in 92Mo. Angular momentum recoupling in the 1g9/2 shell of two protons in 92Mo and two neutron holes in 86Sr are the dominant configurations for these levels. Proton core polarization in 86Sr neutron valence transitions diminishes with increasing multipolarity, indicating the residual interaction weakens with increasing momentum transfer.
Electron impact excitation and assignment of the low-lying electronic states of CO2
Hall, R. I.; Trajmar, S.
1973-01-01
Electron scattering spectra of CO2 are reported in the 7 to 10 eV energy-loss range, at energies of 0.2, 0.35, 0.6, 0.7, and 7.0 eV above threshold, and at a scattering angle of 90 deg. Several new distinct overlapping continua with weak, diffuse bands superimposed are observed to lie in this energy-loss range. The experimental spectra are discussed in the light of recent ab initio configuration-interaction calculations of the vertical transition energies of CO2. The experimental spectra are shown to be consistent with the excitation states of CO2.
Bacalis, Naoum C
2016-01-01
The computation of small concise and comprehensible excited state wave functions is needed because many electronic processes occur in excited states. But since the excited energies are saddle points in the Hilbert space of wave functions, the standard computational methods, based on orthogonality to lower lying approximants, resort to huge and incomprehensible wave functions, otherwise, the truncated wave function is veered away from the exact. The presented variational principle for excited states, Fn, is demonstrated to lead to the correct excited eigenfunction in necessarily small truncated spaces. Using Hylleraas coordinates for He 1S 1s2s, the standard method based on the theorem of Hylleraas - Unheim, and MacDonald, yields misleading main orbitals 1s1s' and needs a series expansion of 27 terms to be corrected, whereas minimizing Fn goes directly to the corect main orbitals, 1s2s, and can be adequately improved by 8 terms. Fn uses crude, rather inaccurate, lower lying approximants and does not need ortho...
Characterization of the low-lying 0$^{+}$ and 2$^{+}$ states of $^{68}$ Ni
Recently, a number of low-lying low-spin states have been firmly identified in $^{68}$Ni; the position of the first excited state (which is a 0$^{+}$ state), the spin and parity of the second excited 0$^{+}$ state and the spin and parity of the second and third 2$^+$ states have been fixed. The identification of these three pairs of 0$^+$ and 2$^+$ states in $^{68}$Ni (Z=28 and N=40) forms ideal tests to validate shell-model calculations and the effective interactions developed for the nickel region but also hints to triple shape coexistence including even strongly deformed structures. The aim of this proposal is to collect detailed spectroscopic data of the low-spin states of $^{68}$Ni (Z=28, N=40) in order to characterize these triple pairs of 0$^+$ and 2$^+$ states. $\\gamma$-branching ratios of the 0$^+$ and 2$^+$ states and the E0 transition strengths as well as the E2 transition rate of the 0$_3^+$ will be obtained using the new ISOLDE decay station that is constructed from an efficient array of germaniu...
Low-lying continuum states of drip-line Oxygen isotopes
Tsukiyama, Koshiroh; Fujimoto, Rintaro
2010-01-01
Low-lying continuum states of exotic oxygen isotopes are studied, by introducing the Continuum-Coupled Shell Model (CCSM) characterized by an infinite wall placed very far and by an interaction for continuum coupling constructed in a close relation to realistic shell-model interaction. Neutron emission spectra from exotic oxygen isotopes are calculated by the doorway-state approach in heavy-ion multi-nucleon transfer reactions. The results agree with experiment remarkably well, as an evidence that the continuum effects are stronger than $\\sim$1 MeV, consistently with the shell evolution in exotic nuclei. The results by this CCSM doorway-state approach are compared with calculations on neutron-scattering resonance peaks made within the CCSM phase-shift approach and also with those obtained in the Gamow shell model, by taking the same interaction. Remarkable similarities in peak energies and certain differences in widths are then obtained.
alpha. - d resonances and the low-lying states of sup 6 Li
Energy Technology Data Exchange (ETDEWEB)
Eskandarian, A.; Afnan, I.R. (School of Physical Sciences, The Flinders University of South Australia, Bedford Park, South Australia 5042 (Australia))
1992-12-01
The low-lying states (below the {sup 3}He-{sup 3}H threshold) of the {sup 6}Li nucleus are generated using three-body models with two-body nonlocal separable interactions between the constituent particles. The positions and widths of the states are determined by searching for the eigenvalues of the kernel of the Faddeev equations in the complex energy plane. When appropriate (for {ital T}=0 states only), the results are compared with a separate determination of these quantities from the {alpha}-{ital d} scattering process. All experimentally observed levels are found. Given that the Coulomb interaction is not included in our calculations, agreement with experiment is favorable for both the positions and the widths of the resonances.
α-d resonances and the low-lying states of 6Li
Eskandarian, A.; Afnan, I. R.
1992-12-01
The low-lying states (below the 3-3H threshold) of the 6Li nucleus are generated using three-body models with two-body nonlocal separable interactions between the constituent particles. The positions and widths of the states are determined by searching for the eigenvalues of the kernel of the Faddeev equations in the complex energy plane. When appropriate (for T=0 states only), the results are compared with a separate determination of these quantities from the α-d scattering process. All experimentally observed levels are found. Given that the Coulomb interaction is not included in our calculations, agreement with experiment is favorable for both the positions and the widths of the resonances.
Performance of Hyperspherical Harmonic Expansionon the Low-lying Pand D States of Helium Atom
Institute of Scientific and Technical Information of China (English)
无
2000-01-01
The wave functions of the n 1,3P (n=2,3,4) and the n 1,3D (n=3,4,5) low-lying states ofthe helium atom are expanded into the complete sets of the symmetrically adapted basis functionsfrom hyperspherical harmonic functions in the angle part and of generalized Laguerre functions inthe radial part respectively, and are then augmented by the simplest type of Jastrow correlationfactor to incorporate electron-nucleus cusp only. The excellent agreement between the presentnonrelativistic eigen-energies and those from the sophisticated configuration interaction (CI)method for the examined states indicates that the hyperspherical harmonic method can also be applied to the P and the D excited states of the helium atom.
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.
Activated singlet exciton fission in a semiconducting polymer.
Musser, Andrew J; Al-Hashimi, Mohammed; Maiuri, Margherita; Brida, Daniele; Heeney, Martin; Cerullo, Giulio; Friend, Richard H; Clark, Jenny
2013-08-28
Singlet exciton fission is a spin-allowed process to generate two triplet excitons from a single absorbed photon. This phenomenon offers great potential in organic photovoltaics, but the mechanism remains poorly understood. Most reports to date have addressed intermolecular fission within small-molecular crystals. However, through appropriate chemical design chromophores capable of intramolecular fission can also be produced. Here we directly observe sub-100 fs activated singlet fission in a semiconducting poly(thienylenevinylene). We demonstrate that fission proceeds directly from the initial 1Bu exciton, contrary to current models that involve the lower-lying 2Ag exciton. In solution, the generated triplet pairs rapidly recombine and decay through the 2Ag state. In films, exciton diffusion breaks this symmetry and we observe long-lived triplets which form charge-transfer states in photovoltaic blends.
Lee, Sangsu; Hwang, Daesub; Jung, Seok Il; Kim, Dongho
2017-02-16
To reveal the applicability of singlet fission processes in perovskite solar cell, we investigated electron transfer from TIPS-pentacene to CH3NH3PbI3 (MAPbI3) perovskite in film phase. Through the observation of the shorter fluorescence lifetime in TIPS-pentacene/MAPbI3 perovskite bilayer film (5 ns) compared with pristine MAPbI3 perovskite film (20 ns), we verified electron-transfer processes between TIPS-pentacene and MAPbI3 perovskite. Furthermore, the observation of singlet fission processes, a faster decay rate, TIPS-pentacene cations, and the analysis of kinetic profiles of the intensity ratio between 500 and 525 nm in the TA spectra of the TIPS-pentacene/MAPbI3 perovskite bilayer film indicate that electron transfer occurs from triplet state of TIPS-pentacene generated by singlet fission processes to MAPbI3 perovskite conduction band. We believe that our results can provide useful information on the design of solar cells sensitized by singlet fission processes and pave the way for new types of perovskite solar cells.
Ab initio study of the low-lying electronic states of the CaO molecule
Energy Technology Data Exchange (ETDEWEB)
Khalil, Hossain; Brites, Vincent; Quere, Frederic Le [Universite Paris-Est, Laboratoire de Modelisation et Simulation Multi Echelle, UMR 8208 CNRS, Batiment Lavoisier, 5 boulevard Descartes, Champs sur Marne, 77454 Marne-la-Vallee, Cedex 2 (France); Leonard, Celine, E-mail: celine.leonard@univ-paris-est.fr [Universite Paris-Est, Laboratoire de Modelisation et Simulation Multi Echelle, UMR 8208 CNRS, Batiment Lavoisier, 5 boulevard Descartes, Champs sur Marne, 77454 Marne-la-Vallee, Cedex 2 (France)
2011-07-28
Graphical abstract: Highly correlated ab initio calculations have been performed for an accurate determination of the electronic structure of the low-lying electronic states of the CaO molecule. The computations are done using the aug-cc-pV5Z basis set for O and the cc-pCV5Z for Ca. The potential energy curves for the molecular states correlating to the lowest three asymptotes are calculated at the CASSCF level. The potential curves of the lowest five molecular states, X{sup 1}{Sigma}{sup +}, a{sup 3}{Pi}, A'{sup 1{Pi}}, b{sup 3}{Sigma}{sup +} and A{sup 1}{Sigma}{sup +}, and the corresponding dipole moment functions have been determined using internally contracted multi-reference configuration interaction approaches. The spectroscopic constants associated with these electronic states are compared to experimental values. The corresponding electronic wavefunctions have also been analyzed using the dipole moment functions. Display Omitted Highlights: {yields} The five lowest electronic states of Cao have been determined ab initio at a high level of accuracy. {yields} Large active space, core-valence correlation and configuration interaction are required. {yields} The multi-configurational nature of the electronic ground state is confirmed as well as its monovalent and divalent ionic nature using dipole moment analysis. {yields} These interacting potentials will serve for future obtention of spin-rovibronic levels. - Abstract: Highly correlated ab initio calculations have been performed for an accurate determination of the electronic structure of the low-lying electronic states of the CaO molecule. The computations are done using the aug-cc-pV5Z basis set for O and the cc-pCV5Z for Ca. The potential energy curves for the molecular states correlating to the lowest three asymptotes are calculated at the CASSCF level. The potential curves of the lowest five molecular states, X{sup 1}{Sigma}{sup +}, a{sup 3}{Pi}, A'{sup 1}{Pi}, b{sup 3}{Sigma}{sup +} and A{sup 1
Ultrafast dynamics of the lowest-lying neutral states in carbon dioxide
Wright, Travis W.; Champenois, Elio G.; Cryan, James P.; Shivaram, Niranjan; Yang, Chan-Shan; Belkacem, Ali
2017-02-01
We present a study of the ultrafast dissociation dynamics of the lowest-lying electronic excited states in CO2 by using ultraviolet (UV) and extreme-ultraviolet (XUV) pulses from high-order harmonic generation. We observe two primary dissociation channels: a direct dissociation channel along the Π1g electronically excited manifold, and a second channel which results from the mixing of electronic states. The direct dissociation channel is found to have a lifetime which is shorter than our experimental resolution, whereas the second channel has a significantly longer lifetime of nearly 200 fs. In this long-lived channel we observe a beating of the vibrational populations with a period of ˜133 fs.
Huber, M G; Chen, W C; Gentile, T R; Hussey, D S; Black, T C; Pushin, D A; Shahi, C B; Wietfeldt, F E; Yang, L
2014-01-01
We report a determination of the n-$^3$He scattering length difference $\\Delta b^{\\prime} = b_{1}^{\\prime}-b_{0}^{\\prime} = $ ($-5.411$ $\\pm$ $0.031$ (statistical) $\\pm$ $0.039$ (systematic)) fm between the triplet and singlet states using a neutron interferometer. This revises our previous result $\\Delta b^{\\prime} = $ (-5.610 $\\pm$ $0.027$ (statistical) $\\pm$ $0.032$ (systematic) fm obtained using the same technique in 2008. This revision is due to a re-analysis of the 2008 experiment that includes a more robust treatment of the phase shift caused by magnetic field gradients near the $^3$He cell. Furthermore, we more than doubled our original data set from 2008 by acquiring six months of additional data in 2013. Both the new data set and a re-analysis of the older data are in good agreement. Scattering lengths of low Z isotopes are valued for use in few-body nuclear effective field theories, provide important tests of modern nuclear potential models and in the case of $^3$He aid in the interpretation of neu...
Communication: DMRG-SCF study of the singlet, triplet, and quintet states of oxo-Mn(Salen)
Energy Technology Data Exchange (ETDEWEB)
Wouters, Sebastian, E-mail: sebastianwouters@gmail.com; Van Speybroeck, Veronique; Van Neck, Dimitri [Center for Molecular Modelling, Ghent University, Technologiepark 903, 9052 Zwijnaarde (Belgium); Bogaerts, Thomas [Center for Molecular Modelling, Ghent University, Technologiepark 903, 9052 Zwijnaarde (Belgium); Center for Ordered Materials, Organometallics and Catalysis, Ghent University, Krijgslaan 281 (S3), 9000 Gent (Belgium); Van Der Voort, Pascal [Center for Ordered Materials, Organometallics and Catalysis, Ghent University, Krijgslaan 281 (S3), 9000 Gent (Belgium)
2014-06-28
We use CHEMPS2, our free open-source spin-adapted implementation of the density matrix renormalization group (DMRG) [S. Wouters, W. Poelmans, P. W. Ayers, and D. Van Neck, Comput. Phys. Commun. 185, 1501 (2014)], to study the lowest singlet, triplet, and quintet states of the oxo-Mn(Salen) complex. We describe how an initial approximate DMRG calculation in a large active space around the Fermi level can be used to obtain a good set of starting orbitals for subsequent complete-active-space or DMRG self-consistent field calculations. This procedure mitigates the need for a localization procedure, followed by a manual selection of the active space. Per multiplicity, the same active space of 28 electrons in 22 orbitals (28e, 22o) is obtained with the 6-31G{sup *}, cc-pVDZ, and ANO-RCC-VDZP basis sets (the latter with DKH2 scalar relativistic corrections). Our calculations provide new insight into the electronic structure of the quintet.
Low-lying electronic states of CuN calculated by MRCI method
Zhang, Shu-Dong; Liu, Chao
2016-10-01
The high accuracy ab initio calculation method of multi-reference configuration interaction (MRCI) is used to compute the low-lying eight electronic states of CuN. The potential energy curves (PECs) of the X3Σ-, 13Π, 23Σ-, 13Δ, 11Δ, 11Σ-, 11Π, and 5Σ- in a range of R = 0.1 nm-0.5 nm are obtained and they are goodly asymptotes to the Cu(2Sg) + N(4Su) and Cu(2Sg) + N(2Du) dissociation limits. All the possible vibrational levels, rotational constants, and spectral constants for the six bound states of X3Σ-, 13Π, 23Σ-, 11Δ, 11Σ-, and 11Π are obtained by solving the radial Schrödinger equation of nuclear motion with the Le Roy provided Level8.0 program. Also the transition dipole moments from the ground state X3Σ- to the excited states 13Π and 23Σ- are calculated and the result indicates that the 23Σ--X3Σ- transition has a much higher transition dipole moment than the 13Π-X3Σ- transition even though the 13Π state is much lower in energy than the 23Σ- state.
N-particle N-level singlet states Properties and applications
Cabello, A
2002-01-01
Three apparently unrelated problems which have no solution using classical tools are described: the ``N-strangers'', ``secret sharing'', and ``liar detection'' problems. A solution for each of them is proposed. Common to the three solutions is the use of quantum states of total spin zero of N spin-(N+1)/2 particles.
Institute of Scientific and Technical Information of China (English)
2007-01-01
The singlet excited state lifetime of the chlorophyll a (Chl a) in cytochrome b6f (Cyt b6f) complex was reported to be shorter than that of free Chl a in methanol, but the value was different for Cyt b6f com-plexes from different sources (~200 and ~600 ps are the two measured results). The present study demonstrated that the singlet excited state lifetime is associated with the detergents n-dodecyl-β-D- maltoside (DDM) and n-octyl-β-D-glucopyranoside (β-OG), but has nothing to do with the different sources of Cyt b6f complexes. Compared with the Cyt b6f dissolved in β-OG, the Cyt b6f in DDM had a lower fluorescence yield, a lower photodegradation rate of Chl a, and a shorter lifetime of Chl a excited state. In short, the singlet excited state lifetime, ~200 ps, of the Chl a in Cyt b6f complex in DDM is closer to the true in vivo.
Highly charged ions in Penning traps, a new tool for resolving low lying isomeric states
Gallant, A T; Brunner, T; Chowdhury, U; Ettenauer, S; Simon, V V; Mané, E; Simon, M C; Andreoiu, C; Delheij, P; Gwinner, G; Pearson, M R; Ringle, R; Dilling, J
2011-01-01
The use of highly charged ions greatly increases the precision and resolving power, in particular for short-lived species produced at on-line radio-isotope beam facilities, achievable with Penning trap mass spectrometers. This increase in resolving power provides a new and unique access to resolving low-lying long-lived ($T_{1/2} > 50$ ms) nuclear isomers. Recently, the $111.19(22)$ keV (determined from $\\gamma$-ray spectroscopy) isomeric state in $^{78}$Rb has been resolved from the ground state, in a charge state of $q=8+$ with the TITAN Penning trap at the TRIUMF-ISAC facility. The energy level of the isomer was measured to be $108.7(6.4)$ keV above the ground state. The extracted masses for both the ground and isomeric states, and their difference, agree with the AME2003 and Nuclear Data Sheet values. This proof of principle measurement demonstrates the feasibility of using Penning trap mass spectrometers coupled to charge breeders to study nuclear isomers and opens a new route for isomer searches.
Low-Lying Resonance States of Slow Electron Collisions With Atomic Oxygen
Institute of Scientific and Technical Information of China (English)
吴建华; 袁建民
2003-01-01
A 39-target state close-coupling calculation of low-energy electron scattering from atomic oxygen is carried out with core-valence electron correlation by using R-matrix method. It is shown that the elastic cross section has a huge and sharp increase with the electron energy going down below 1eV. This remarkable structure is attributed to a few very low-lying potential resonances and the features of these resonances are given with partial cross sections. It is also shown that after considering excitations of two electrons from 2s shell, the three lowest atomic energy levels are in agreement with experimental results better than that just considering excitations of two electrons from the 2p shell as well as only one electron from the 2s shell. Elastic and two excitation (3P → 1 D and 3p → 1S) cross sections are given and compared with the other theoretical and experimental results.
Indian Academy of Sciences (India)
Anjan Chattopadhyay
2012-09-01
Semiempirical and ab initio-based CI methods have been employed to study the low-lying electronic states of 2,4-pentadien-1-iminium cation and its N-substituted analogues with electron-donating (methyl, isopropyl) and electron-withdrawing (fluoromethyl) groups on nitrogen. Variations of the dihedral angles (Γ3, Γ4) of the ground state have given the global minima and global maxima at (180°, 180°) and (90°, 0°) conformations, respectively, with some exceptions in the case of fluoromethyl compound. Increase in the +I effect on nitrogen shifts the TICT conical intersection point away from the 90° (Γ3 dihedral angle) value, when the Γ4 value is kept fixed at 180°. Transition moment values of the allowed S0(1A -like) → S1 (2B-like) transitions are expectedly higher than the forbidden S0(1A -like) → S2(2A -like) transitions by almost 5.6 D. Radiative lifetime values of the first excited states are calculated to be around 215 ps for all the four compounds. At (180°, 180°) conformation the vertical excitation energy (VEE) between the S0 and S1 states of the 2,4-pentadieniminium cation is found to be 3.3 eV, which corresponds to the absorption wavelength value of roughly 375 nm. The VEE value increases with substituents having +I effect on nitrogen, while for the fluoromethyl compound it is calculated to be around 2.85 eV. The energy gap between the first two excited singlet states is found to have the least value in the isopropyl-substituted compound, where the S2 state contains a huge contribution from the HOMO2→LUMO2 configuration.
Nuclear orientation of 144Pm in the electronic singlet ground state system PrIn 3
Vermeulen, G. A.; Greidanus, F. J. A. M.; Hunik, R.; Huiskamp, W. J.
1980-04-01
The gamma-ray anisotropy of 144Pm in the Van Vleck paramagnet PrIn 3 is investigated both theoretically and experimentally. A simple model, which accounts for the essential experimental features is proposed. The purpose of this model is to extract the exchange interaction between the Pm ion and its nearest Pr neighbours and the crystal field splitting of the Pm ions. Both, the Pr and Pm ions have non-magnetic ground states in which magnetism is induced by external magnetic fields. Therefore, the interaction between the external magnetic field and the Pm nuclei is enhanced. We find an enhancement factor, к = 220. This enhancement is mainly induced by exchange interactions and for fields larger than 0.5 T there are already strong non-linear effects.
Potential energy curves for the ground and low-lying excited states of CuAg
Energy Technology Data Exchange (ETDEWEB)
Alizadeh, Davood; Shayesteh, Alireza, E-mail: jamshidi@ccerci.ac.ir, E-mail: ashayesteh@ut.ac.ir [School of Chemistry, College of Science, University of Tehran, 14176 Tehran (Iran, Islamic Republic of); Jamshidi, Zahra, E-mail: jamshidi@ccerci.ac.ir, E-mail: ashayesteh@ut.ac.ir [Chemistry and Chemical Engineering Research Center of Iran, 14335-186 Tehran (Iran, Islamic Republic of)
2014-10-21
The ground and low-lying excited states of heteronuclear diatomic CuAg are examined by multi-reference configuration interaction (MRCI) method. Relativistic effects were treated and probed in two steps. Scalar terms were considered using the spin-free DKH Hamiltonian as a priori and spin-orbit coupling was calculated perturbatively via the spin-orbit terms of the Breit-Pauli Hamiltonian based on MRCI wavefunctions. Potential energy curves of the spin-free states and their corresponding Ω components correlating with the separated atom limits {sup 2}S(Cu) + {sup 2}S(Ag) and {sup 2}D(Cu) + {sup 2}S(Ag) are obtained. The results are in fine agreement with the experimental measurements and tentative conclusions for the ion-pair B0{sup +} state are confirmed by our theoretical calculations. Illustrative results are presented to reveal the relative importance and magnitude of the scalar and spin-orbit effects on the spectroscopic properties of this molecule. Time dependent density functional theory calculations, using the LDA, BLYP, B3LYP, and SAOP functionals have been carried out for CuAg and the accuracy of TD-DFT has been compared with ab initio results.
Dirac Coupled Channel Analyses of the high-lying excited states at $^{22}$Ne(p,p$'$)$^{22}$Ne
Shim, Sugie
2015-01-01
Dirac phenomenological coupled channel analyses are performed using an optical potential model for the high-lying excited vibrational states at 800 MeV unpolarized proton inelastic scatterings from $^{22}$Ne nucleus. Lorentz-covariant scalar and time-like vector potentials are used as direct optical potentials and the first-order vibrational collective model is used for the transition optical potentials to describe the high-lying excited vibrational collective states. The complicated Dirac coupled channel equations are solved phenomenologically using a sequential iteration method by varying the optical potential and the deformation parameters. Relativistic Dirac coupled channel calculations are able to describe the high-lying excited states of the vibrational bands in $^{22}$Ne clearly better than the nonrelativistic coupled channel calculations. The channel-coupling effects of the multistep process for the excited states of the vibrational bands are investigated. The deformation parameters obtained from the ...
DEFF Research Database (Denmark)
Shim, Irene; Gingerich, K. A.
2000-01-01
The three lowest-lying electronic states of RuC, (1)Sigma(+), (3)Delta, and (1)Delta, have been investigated by performing all-electron ab initio multi-configuration self-consistent-field (CASSCF) and multi-reference configuration interaction (MRCI) calculations including relativistic corrections....... The electronic ground state is derived as (1)Sigma(+) with the spectroscopic constants r(e) = 1.616 Angstrom and omega(e) = 1085 cm(-1). The lowest-lying excited state, (3)Delta, has r(e) = 1.632 Angstrom, omega(e) = 1063 cm(-1), and T-e = 912 cm(-1). These results are consistent with recent spectroscopic values....... The chemical bonds in all three lowest-lying states are triple bonds composed of one sigma and two pi bonds. (C) 2000 Elsevier Science B.V. All rights reserved....
Differential magnetometry with multiparticle singlets
Urizar-Lanz, Inigo; Egusquiza, Inigo; Mitchell, Morgan W; Toth, Geza
2012-01-01
We present a method for measuring the magnetic field gradient with singlets realized with spin-1/2 particles. While the singlet state does not change under the influence of homogenous magnetic fields, the variance of the collective spin components start to grow under a field gradient. We compute the dynamics of this variance analytically for a chain of spins and also for an ensemble of particles with a given density distribution. We calculate an upper bound on how exactly the field gradient can be estimated from the measured data. The proposal is relevant for cold atomic ensembles where multiparticle singlet states can be prepared by spin squeezing and the differential magnetometry can be carried out.
Theoretical spectroscopic constants for the low-lying states of the oxides and sulfides of Mo and Tc
Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Siegbahn, Per E. M.
1989-01-01
Spectroscopic results were determined for the ground and low-lying states of the oxides and sulfides of Mo and Tc, using the single-reference-based modified coupled pair functional method of Ahlrichs et al. (1985) and Chong et al. (1986) and the multireference-based state-averaged CASSCF/MRCI method. Spectroscopic constants, dipole moments, Mulliken populations, and radiative lifetimes were calculated for selected low-lying states of these molecular systems. The spectroscopy of the MoS and TcS molecules was found to be quite analogous to the corresponding oxides.
Jafarizadeh, M. A.; Majarshin, A. Jalili; Fouladi, N.
2016-11-01
In order to investigate negative parity states, it is necessary to consider negative parity-bosons additionally to the usual s- and d-bosons. The dipole and octupole degrees of freedom are essential to describe the observed low-lying collective states with negative parity. An extended interacting boson model (IBM) that describes pairing interactions among s, p, d and f-boson based on affine SU(1, 1) Lie algebra in the quantum phase transition (QPT) field, such as spd-IBM, sdf-IBM and spdf-IBM, is composed based on algebraic structure. In this paper, a solvable extended transitional Hamiltonian based on affine SU(1, 1) Lie algebra is proposed to describe low-lying positive and negative parity states between the spherical and deformed gamma-unstable shape. Three model of new algebraic solution for even-even nuclei are introduced. Numerical extraction to low-lying energy levels and transition rates within the control parameters of this evaluated Hamiltonian are presented for various N values. We reproduced the positive and negative parity states and our calculations suggest that the results of spdf-IBM are better than spd-IBM and sdf-IBM in this literature. By reproducing the experimental results, the method based on signature of the phase transition such as level crossing in the lowest excited states is used to provide a better description of Ru isotopes in this transitional region.
Energy Technology Data Exchange (ETDEWEB)
Winghart, Marc-Oliver, E-mail: marc-oliver.winghart@kit.edu; Unterreiner, Andreas-Neil [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Yang, Ji-Ping [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); School of Sciences, Hefei University of Technology, Hefei 230009 (China); Vonderach, Matthias [Centre for Proteome Research, Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Huang, Dao-Ling; Wang, Lai-Sheng [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States); Kruppa, Sebastian; Riehn, Christoph [Fachbereich Chemie und Landesforschungszentrum OPTIMAS, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Kappes, Manfred M., E-mail: manfred.kappes@kit.edu [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe (Germany)
2016-02-07
Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet {sup 1}A{sub 2u} state and concomitant rise in population of the triplet {sup 3}A{sub 2u} state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet {sup 1}A{sub 2u} state takes only a few picoseconds, ESETD from the triplet {sup 3}A{sub 2u} state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} is the first example of a photoexcited multianion for which ESETD has been observed following ISC.
Theoretical calculation of low-lying states of NaAr and NaXe
Laskowski, B. C.; Langhoff, S. R.; Stallcop, J. R.
1981-01-01
Potential curves as well as dipole moments and linking transition moments are calculated for the ground X 2 Sigma + and low lying excited A 2 Pi, B 2 Sigma +, C 2 Sigma +, (4) 2 Sigma +, (2) 2 Pi and (1) 2 Delta states of NaAr and NaXe. Calculations are performed using a self-consistent field plus configuration-interaction procedure with the core electrons replaced by an ab initio effective core potential. The potential curves obtained are found to be considerably less repulsive than the semiempirical curves of Pascale and Vandeplanque (1974) and to agree well with existing experimental data, although the binding energies of those states having potential minima due to van der Waals interactions are underestimated. Emission bands are also calculated for the X 2 Sigma + - C 2 Sigma + excimer transitions of NaAr and NaXe using the calculated transition moments and potential curves, and shown to agree well with experiment on the short-wavelength side of the maximum.
Theoretical studies of the low-lying states of ScO, ScS, VO, and VS
Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.
1986-01-01
Bonding in the low-lying states of ScO, ScS, VO, and VS is theoretically studied. Excellent agreement is obtained with experimental spectroscopic constants for the low-lying states of ScO and VO. The results for VS and ScS show that the bonding in the oxides and sulfides is similar, but that the smaller electronegativity in S leads to a smaller ionic component in the bonding. The computed D0 of the sulfides are about 86 percent of the corresponding oxides, and the low-lying excited states are lower in the sulfides than in the corresponding oxides. The CPF method is shown to be an accurate and cost-effective method for obtaining reliable spectroscopic constants for these systems.
Low-Lying States of the A+B-A+B- Coulomb Systems in Two-Dimensional Quantum Dots
Institute of Scientific and Technical Information of China (English)
XIE Wen-Fang
2001-01-01
The features of the low-lying spectra of four-body A+B-A+B- systems have been deduced based on symmetry. Using the method of few-body physics, we calculate the energy spectra of A + B- A + B- systems in a harmonic quantum dot. We find that the biexciton in a two-dimensional quantum dot may have other bound excited states and the quantum mechanical symmetry plays a crucialrole in determining the energy levels and structures of the low-lying states.
On the low-lying states of WO - A comparison with CrO and MoO
Nelin, C. J.; Bauschlicher, C. W., Jr.
1985-01-01
The four low-lying states of WO were investigated and compared with similar states of CrO and MoO. For all these systems the ground state is 5 Pi, but the ordering of the upper states is different between WO and either CrO or MoO. The difference in the state ordering arises in part from the fact that in WO all of the states are formed from W(+) in a d4S1 configuration, whereas in both CrO and MoO some states are formed from the d5 configuration and others from the d4S1 configuration.
Deng, Bin; Simental, Anabel; Lutz, Patrick; Shaheen, George; Chaiken, Joseph
2012-01-01
Nonenzymatic glycation and oxidation of ubiquitous proteins in vivo leads to irreversible formation of advanced glycation end products (AGEs). Due to their relatively long half life and low clearance rate AGEs tend to accumulate within static tissues and the circulatory system. Spectra obtained using 830 nm near-infrared (NIR) excitation suggest that the so-called "autofluorescence" from all tissues has a finite number of sources but the fact that senior and diabetic subjects produce more than other members of the general population suggests that a significant portion of the total autofluorescence from all sources originates from AGEs. Using pentosidine generated in a reaction mixture as described by Monnier as representative, an in vitro study unveiled very similar fluorescence and photobleaching pattern as observed for autofluorescence in vivo. A series of oxygen, air and argon purging experiments on the pentosidine-generating reaction mixture suggests that pentosidine is a singlet oxygen sensitizer and secondary reactions between the pentosidine itself and/or other fluorophores and the photosensitized singlet oxygen explain the observed photobleaching. Ab initio Gaussian calculations on pentosidine reveal the existence of low-lying triplet excited states required for the sensitization of ground state oxygen. A commercially available product known as singlet oxygen sensor green (SOSG) that specifically serves as a singlet oxygen detection reagent confirms the generation of singlet oxygen from NIR irradiated pentosidine trimixture. This study provides one definite chemical mechanism for understanding in vivo human skin autofluorescence and photobleaching.
Diphotons from an Electroweak Triplet-Singlet
Energy Technology Data Exchange (ETDEWEB)
Howe, Kiel [Fermilab; Knapen, Simon [UC, Berkeley; Robinson, Dean J. [UC, Berkeley
2016-03-29
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 $W\\gamma$ 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.
Role of 'quasiparticle x phonon' components in gamma-decay of high-lying states
Energy Technology Data Exchange (ETDEWEB)
Ponomarev, V.Yu.; Soloviev, V.G.; Vdovin, A.I.; Stoyanov, C.
1987-01-15
The ..gamma.. decay rates of highly excited nuclear states of odd-mass nuclei into the low-lying one-quasiparticle states are calculated in a microscopic way. We conclude that not only the one quasiparticle component but also ''quasiparticle x phonon'' components of the wave function of highly excited states can play an important role in their ..gamma.. decay.
Theoretical study of the low-lying electronic states of ZnO and ZnS
Bauschlicher, C. W., Jr.; Langhoff, S. R.
1986-01-01
Theoretical spectroscopic constants and dipole moments are determined for the 1 Sigma(+), 1,3 Pi, and 3 Sigma(+) states of ZnO and ZnS, using extended Gaussian basis sets and incorporating correlation using both configuration-interaction and coupled pair (CPF) methods. Relativistic corrections (Darwin plus mass velocity), included using first-order perturbation theory, are relatively small. At the CPF level, both ZnO and ZnS have 1 Sigma(+) ground states, with the 3 Pi state lying 209 and 2075/cm higher, respectively. The 3 Sigma(+) state lies about 1.5 eV higher in ZnO and 2.1 eV higher in ZnS. The 1,3 Pi states are relatively close together since the exchange splitting is small with the sigma electron localized on Zn and the pi electron on oxygen (or sulfur).
Institute of Scientific and Technical Information of China (English)
CHEN XiaoBo; ZHAO XiaoHui; ZHANG JianPing; LI LiangBi; KUANG TingYun
2007-01-01
The singlet excited state lifetime of the chlorophyll a (Chi a) in cytochrome b6f (Cyt b6f) complex was reported to be shorter than that of free Chl a in methanol, but the value was different for Cyt b6f complexes from different sources (～200 and ～600 ps are the two measured results). The present study demonstrated that the singiet excited state lifetime is associated with the detergents n-dodecyl-β-D-maltoside (DDM) and n-octyl-β-D-glucopyranoside (β-OG), but has nothing to do with the different sources of Cyt b6f complexes. Compared with the Cyt b6f dissolved in β-OG, the Cyt b6f in DDM had a lower fluorescence yield, a lower photodegradation rate of Chl a, and a shorter lifetime of Chl a excited state. In short, the singlet excited state lifetime, ～200 ps, of the Chl a in Cyt b6f complex in DDM is closer to the true in vivo.
Heyman, Gail D.; Luu, Diem H.; Lee, Kang
2009-01-01
The present set of studies identifies the phenomenon of "parenting by lying", in which parents lie to their children as a means of influencing their emotional states and behaviour. In Study 1, undergraduates (n = 127) reported that their parents had lied to them while maintaining a concurrent emphasis on the importance of honesty. In Study 2 (n =…
Directory of Open Access Journals (Sweden)
Marie Asano
2014-08-01
Full Text Available We examined the effects of caffeic acid (CA and related compounds on 7-carboxyheptyl radical formation. This analysis was performed using a standard D2O reaction mixture containing 4.3 mM oleic acid, 25 μM flavin mononucleotide (FMN, 160 mM phosphate buffer (pH 7.4, 10 mM cholic acid, 100 mM α-(4-pyridyl-1-oxide-N-tert-butylnitrone, and 1 mM Fe(SO42(NH42 during irradiation with 7.8 J/cm2 at 436 nm. 7-Carboxyheptyl radical formation was inhibited by CA, catechol, gallic acid, chlorogenic acid, ferulic acid, noradrenalin, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid. Quinic acid, benzoic acid, and p-anisic acid had no effect on radical formation. These results suggest that a phenol moiety is essential for these inhibitory effects. The fluorescence intensity of FMN decreased by 69% ± 2% after CA addition, suggesting that CA quenches the singlet excited state of FMN. When 1 mM CA was added to a standard reaction mixture containing 25 μM FMN, 140 mM phosphate buffer (pH 7.4, and 10 mM 4-oxo-2,2,6,6-tetramethylpiperidine, the electron spin resonance signal of 4-oxo-2,2,6,6-tetramethylpiperidinooxy disappeared. This finding suggests that singlet oxygen was scavenged completely by CA. Therefore, CA appears to inhibit 7-carboxyheptyl radical formation by scavenging singlet oxygen and quenching the excited state of FMN.
Low-lying T=0 states in the odd–odd N=Z nucleus {sup 62}Ga
Energy Technology Data Exchange (ETDEWEB)
David, H.M., E-mail: hdavid@anl.gov [University of Edinburgh, Edinburgh, EH9 3JZ (United Kingdom); Woods, P.J.; Lotay, G. [University of Edinburgh, Edinburgh, EH9 3JZ (United Kingdom); Seweryniak, D.; Albers, M.; Alcorta, M.; Carpenter, M.P. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Chiara, C.J. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States); University of Maryland, College Park, MD 20742 (United States); Davinson, T.; Doherty, D.T. [University of Edinburgh, Edinburgh, EH9 3JZ (United Kingdom); Hoffman, C.R.; Janssens, R.V.F.; Lauritsen, T.; Rogers, A.M.; Zhu, S. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States)
2013-11-04
New, low-lying levels in the odd–odd, N=Z nucleus {sup 62}Ga have been identified using a sensitive technique, where in-beam γ rays from short-lived nuclei are tagged with β decays following recoil mass identification. A comparison of the results with shell-model and IBM-4 calculations demonstrates good agreement between theory and experiment, with the majority of predicted low-lying, low-spin T=0 states now identified. There is a dramatic change in the level density at low excitation energies for the N=Z nucleus {sup 62}Ga when compared with neighbouring odd–odd Ga isotopes where, in contrast, the low-lying level structure is dominated by configurations with T=1 pairing interactions between excess neutrons. This illustrates the distinctively different aspects of nuclear structure exhibited by nuclei with N=Z.
Energy Technology Data Exchange (ETDEWEB)
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.
Energy Technology Data Exchange (ETDEWEB)
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.
Low-lying isomeric state in {sup 80}Ga from the {beta}{sup -} decay of {sup 80}Zn
Energy Technology Data Exchange (ETDEWEB)
LicA, R.; Marginean, N.; Ghita, D.G. [Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest (Romania); and others
2012-10-20
A new level scheme was constructed for {sup 80}Ga which is significantly different from the one previously reported. The excitation energy of a new low-lying state recently reported in [2] was identified at 22.4 keV. Properties of the level scheme suggest that the ground state has spin J = 6 and the first excited state has spin J = 3. The spin assignments are in agreement with laser spectroscopy values previously measured. Our work provides the first evidence for the J = 6 being the ground state.
Jacobson, Nathan
1979-01-01
Lie group theory, developed by M. Sophus Lie in the 19th century, ranks among the more important developments in modern mathematics. Lie algebras comprise a significant part of Lie group theory and are being actively studied today. This book, by Professor Nathan Jacobson of Yale, is the definitive treatment of the subject and can be used as a textbook for graduate courses.Chapter I introduces basic concepts that are necessary for an understanding of structure theory, while the following three chapters present the theory itself: solvable and nilpotent Lie algebras, Carlan's criterion and its
Sasabe, Norimasa; Tonai, Hironori; Uozumi, Takayuki
2017-09-01
The spectral change in the 3d resonant X-ray inelastic scattering (RIXS) induced by the spin-state transition between Kondo singlet (KS) and localized spin (LS) state is theoretically investigated for γ-like Ce intermetallics by means of a single impurity Anderson model. The basis configurations with an electron-hole pair are included in the calculation within the configuration interaction scheme, in addition to the intra-atomic full multiplet coupling of the Ce impurity. A distinct spectral change is found across the KS-LS transition in the RIXS excited at the charge-transfer satellite of the 3d X-ray absorption spectrum (XAS) under a polarized geometry. In contrast, the 3d XAS and RIXS spectra under a depolarized geometry are rather insensitive to the spin-state transition.
Energy Technology Data Exchange (ETDEWEB)
Dombek, M. G.
1977-12-01
Energy curves are determined for the lowest singlet and triplet states of the HNO molecule. The geometry is varied in that the hydrogen moves through 13 positions around the NO core to describe the isomerization reaction HNO yields HON. Quantitatively determined are the stable and metastable equilibrium positions in both states, the energy differences between these two equilibrium positions and between the two states, and the barriers with respect to isomerization. The calculations are carried out using a novel configuration interaction approach called the Full Optimized Reaction Space method, which involves multiconfigurational self-consistent field calculations as an integral part. In order to interpret the bonding changes occurring during the reaction, a novel type of orbital is developed and calculated. These are called Directed Localized Reaction Orbitals. With their help it proves possible to give an interpretation of the isomerization in terms of concepts which fit chemical intuition.
Filatov, Mikhail A.
2017-04-14
Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of the alkyl substituents in the BODIPY subunit defines the site of 1O2 addition. Novel bis- and tetraepoxides and bicyclic acetal products, arising from rearrangements of anthracene endoperoxides were isolated and characterized. 1O2 generation by BADs in living cells enables visualization of the dyads distribution, promising new imaging applications.
Energy Technology Data Exchange (ETDEWEB)
Karmakar, Shreetama; Mukhopadhyay, Deb Pratim; Chakraborty, Tapas, E-mail: pctc@iacs.res.in [Physical Chemistry Department, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)
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
Institute of Scientific and Technical Information of China (English)
郑雨军; 丁世良
2000-01-01
The vibrational excitations of bent triatomic molecules are studied by using Lie algebra. The RMS error of fitting 30 spectroscopic data is 1.66 cm-1 for SO2. The results show that the expansion of a molecular algebraic Hamiltonian can well describe the experimental data. And the total vibrational levels can be calculated using this Hamiltonian. At the same time, the potential energy surface can also be obtained with the algebraic Hamiltonian.
Langhoff, Stephen R.; Pettersson, Lars G. M.; Bauschlicher, Charles W., Jr.; Partridge, Harry
1987-01-01
A systematic analysis of the low-lying states of all of the second-row transition metal (TM) hydrides except CdH is reported. The calculations included the dominant relativistic contributions through the use of the relativistic effective core potentials of Hay and Wadt (1985). Electron correlation was incorporated, using single-plus-double configuration interaction, the coupled pair functional (CPF) formalism of Ahlrichs et al. (1985), and the Chong and Langhoff (1986) modified version of the CPF method. The spectroscopic parameters D(e), r(e), and mu(e) determined for the low-lying states are compared with the available experimental data and previous theoretical results. In contrast to the first-row TM hydrides studied earlier (Chong et al., 1986), the spectroscopic constants for the second-row TM hydrides were found to be much less sensitive to the level of correlation treatment.
Langhoff, Stephen R.; Pettersson, Lars G. M.; Bauschlicher, Charles W., Jr.; Partridge, Harry
1987-01-01
A systematic analysis of the low-lying states of all of the second-row transition metal (TM) hydrides except CdH is reported. The calculations included the dominant relativistic contributions through the use of the relativistic effective core potentials of Hay and Wadt (1985). Electron correlation was incorporated, using single-plus-double configuration interaction, the coupled pair functional (CPF) formalism of Ahlrichs et al. (1985), and the Chong and Langhoff (1986) modified version of the CPF method. The spectroscopic parameters D(e), r(e), and mu(e) determined for the low-lying states are compared with the available experimental data and previous theoretical results. In contrast to the first-row TM hydrides studied earlier (Chong et al., 1986), the spectroscopic constants for the second-row TM hydrides were found to be much less sensitive to the level of correlation treatment.
Laser-induced fluorescence spectroscopy of jet-cooled TiC: Observation of low-lying 1Σ+ states
Nakhate, S. G.; Mukund, Sheo; Bhattacharyya, Soumen
2017-07-01
The TiC has been investigated using laser-induced fluorescence spectroscopy. The a1Σ+, b1Σ+, and c1Σ+ states are found to lie respectively at T0 = 319.3, 786.0, and 1407.2 cm-1 and have internuclear distances respectively of r0 = 1.6607, 1.6906, and 1.6927 Å. Similar r0 values of the b1Σ+ and c1Σ+ states with that of the X3Σ+ state (1.6953 Å) indicate that either of these states could be isocofigurational to the ground state. Dispersed fluorescence suggests reassignment of the 3Π1 state to a mixed state with dominant 1Π character. Higher spectral resolution of the 1Π-X3Σ+ band provided improved molecular constants.
Papi, Paolo; Advances in Lie Superalgebras
2014-01-01
The volume is the outcome of the conference "Lie superalgebras," which was held at the Istituto Nazionale di Alta Matematica, in 2012. The conference gathered many specialists in the subject, and the talks held provided comprehensive insights into the newest trends in research on Lie superalgebras (and related topics like vertex algebras, representation theory and supergeometry). The book contains contributions of many leading esperts in the field and provides a complete account of the newest trends in research on Lie Superalgebras.
Institute of Scientific and Technical Information of China (English)
曹泽星; 吴玮; 张乾二
1997-01-01
Based on the correspondence of the molecular orbital theory and valence bond theory to the description of chemical bonds,the ah imtio valence bond (VB) calculations of the low-lying states of diatomic molecules arc realized.The calculation results for the low-lying states of B2 show that the VB calculation has clear-cut physical significance,and its simulation of the behavior of the potential energy surface about the equilibrium position is superior to that of the molecular orbital theory.The valence bond calculation involving only a few bonded tableaus can correctly re fleet the effect of electronic correlation.
Energy Technology Data Exchange (ETDEWEB)
Hauschild, K.; Bernstein, L.A.; Becker, J.A. [Lawrence Livermore National Lab., CA (United States)] [and others
1996-12-31
The observation of one-step `primary` gamma-ray transitions directly linking the superdeformed (SD) states to the normal deformed (ND) low-lying states of known excitation energies (E{sub x}), spins and parities (J{sup {pi}}) is crucial to determining the E{sub x} and J{sup {pi}} of the SD states. With this knowledge one can begin to address some of the outstanding problems associated with SD nuclei, such as the identical band issue, and one can also place more stringent restrictions on theoretical calculations which predict SD states and their properties. Brinkman, et al., used the early implementation of the GAMMASPHERE spectrometer array (32 detectors) and proposed a single, candidate {gamma} ray linking the {sup 194}Pb yrast SD band to the low-lying ND states in {sup 194}Pb. Using 55 detectors in the GAMMASPHERE array Khoo, et al., observed multiple links between the yrast SD band in {sup 194}Hg and the low-lying level scheme and conclusively determined E{sub x} and J of the yrast SD states. Here the authors report on an experiment in which Gammasphere with 88 detectors was used and the E{sub x} and J{sup {pi}} values of the yrast SD states in {sup 194}Pb were uniquely determined. Twelve one-step linking transitions between the yrast SD band and low-lying states in {sup 194}Pb have been identified, including the transition proposed by Brinkman. These transitions have been placed in the level scheme of {sup 194}Pb using coincidence relationships and agreements between the energies of the primary transitions and the energy differences in level spacings. Furthermore, measurements of angular asymmetries have yielded the multipolarities of the primaries which have allowed J{sup {pi}} assignments of the {sup 194}Pb SD states to be unambiguously determined for the first time without a priori assumptions about the character of SD bands. A study performed in parallel to this work using the EUROGAM-II array reports similar, but somewhat less extensive, results.
Study of the γ decay of high-lying states in 208Pb via inelastic scattering of 17O ions
Directory of Open Access Journals (Sweden)
Crespi F.C.L.
2014-03-01
Full Text Available A measurement of the high-lying states in 208Pb has been made using 17O beams at 20 MeV/u. The gamma decay following inelastic excitation was measured with the detector system AGATA Demonstrator based on segmented HPGe detectors, coupled to an array of large volume LaBr3:Ce scintillators and to an array of Si detectors. Preliminary results in comparison with (γ,γ’ data, for states in the 5-8 MeV energy interval, are presented.
Study of the γ decay of high-lying states in 208Pb via inelastic scattering of 17O ions
Crespi, F. C. L.; Kmiecik, M.; Bracco, A.; Leoni, S.; Maj, A.; Benzoni, G.; Blasi, N.; Boiano, C.; Bottoni, S.; Brambilla, S.; Camera, F.; Ceruti, S.; Giaz, A.; Million, B.; Morales, A. I.; Nicolini, R.; Pellegri, L.; Riboldi, S.; Vandone, V.; Wieland, O.; Bednarczyk, P.; Ciemala, M.; Grebosz, J.; Krzysiek, M.; Mazurek, K.; Zieblinski, M.; Bazzacco, D.; Bellato, M.; Birkenbach, B.; Bortolato, D.; Calore, E.; De Angelis, G.; Farnea, E.; Gadea, A.; Görgen, A.; Gottardo, A.; Isocrate, R.; Lenzi, S.; Lunardi, S.; Mengoni, D.; Michelagnoli, C.; Molini, P.; Napoli, D. R.; Recchia, F.; Sahin, E.; Siebeck, B.; Siem, S.; Ur, C.; Valiente Dobon, J. J.
2014-03-01
A measurement of the high-lying states in 208Pb has been made using 17O beams at 20 MeV/u. The gamma decay following inelastic excitation was measured with the detector system AGATA Demonstrator based on segmented HPGe detectors, coupled to an array of large volume LaBr3:Ce scintillators and to an array of Si detectors. Preliminary results in comparison with (γ,γ') data, for states in the 5-8 MeV energy interval, are presented.
Sp ectroscopy of Low-lying States in Odd-Z Odd-A Nuclei Beyond Lead
Institute of Scientific and Technical Information of China (English)
U Jakobsson; S Juutinen; A Herzan; J Konki; M Leino; M Mallaburn; J Pakarinen; P Papadakis; J Partanen; P Rahkila; M Sandzelius; J Uusitalo; J Saren; C Scholey; J Sorri; S Stolze; K Auranen; H Badran; B Cederwall; D M Cox; T Grahn; P T Greenlees; R Julin
2016-01-01
Low-lying states in odd-Z odd-mass nuclei at the proton drip-line beyond lead have recently been studied through fusion-evaporation reactions using a gas-filled recoil separator. Isomeric 1/2+ and 13/2+ states have been observed in odd-mass astatine and francium nuclei. The systematic behaviour of the level energies of these states have been studied and a similarity between the 1/2+ state in astatine and francium has been found. Furthermore, the 13/2+ state has been observed in the francium nuclei with an oblate behaviour suggesting a coupling of the i13/2 proton to the 2p−2h intruder excitation.
Brics, M
2013-01-01
Favorably scaling numerical time-dependent many-electron techniques such as time-dependent density functional theory (TDDFT) with adiabatic exchange-correlation potentials typically fail in capturing highly correlated electron dynamics. We propose a method based on natural orbitals, i.e., the eigenfunctions of the one-body reduced density matrix, that is almost as inexpensive numerically as adiabatic TDDFT, but which is capable of describing correlated phenomena such as doubly excited states, autoionization, Fano profiles in the photoelectron spectra, and strong-field ionization in general. Equations of motion (EOM) for natural orbitals and their occupation numbers have been derived earlier. We show that by using renormalized natural orbitals (RNO) both can be combined into one equation governed by a hermitian effective Hamiltonian. We specialize on the two-electron spin-singlet system, known as being a "worst case" testing ground for TDDFT, and employ the widely used, numerically exactly solvable, one-dimens...
Bauschlicher, C. W., Jr.; Silver, D. M.; Yarkony, D. R.
1980-01-01
The paper presents the multiconfiguration-self-consistent (MCSCF) and configuration state functions (CSF) for the low-lying electronic states of MgO. It was shown that simple description of these states was possible provided the 1 Sigma(+) states are individually optimized at the MCSCF level, noting that the 1(3 Sigma)(+) and 2(1 Sigma)(+) states which nominally result from the same electron occupation are separated energetically. The molecular orbitals obtained at this level of approximation should provide a useful starting point for extended configuration interaction calculations since they have been optimized for the particular states of interest.
Bauschlicher, C. W., Jr.; Silver, D. M.; Yarkony, D. R.
1980-01-01
The paper presents the multiconfiguration-self-consistent (MCSCF) and configuration state functions (CSF) for the low-lying electronic states of MgO. It was shown that simple description of these states was possible provided the 1 Sigma(+) states are individually optimized at the MCSCF level, noting that the 1(3 Sigma)(+) and 2(1 Sigma)(+) states which nominally result from the same electron occupation are separated energetically. The molecular orbitals obtained at this level of approximation should provide a useful starting point for extended configuration interaction calculations since they have been optimized for the particular states of interest.
Electron impact excitation and assignment of the low-lying electronic states of N2O
Hall, R. I.; Chutjian, A.; Trajmar, S.
1973-01-01
Electron scattering spectra of nitrous oxide are reported in the 5- to 10-eV energy-loss range at scattering angles of 20, 30, 90, and 130 deg at a residual energy of 7.0 eV; and at residual energies of 10.0, 2.0, 1.0, 0.6, and 0.2 eV at a scattering angle of 90 deg. Several new distinct and overlapping continua are observed to lie in this energy-loss range. The experimental spectra are discussed in the light of semiempirical INDO calculations of Chutjian and Segal (1972) of the vertical transition energies of N2O. An assignment of the symmetries of the observed excitations consistent with the experimental and theoretical data is suggested.
Electron-impact excitation of the low-lying electronic states of HCN
Chutjian, A.; Tanaka, H.; Srivastava, S. K.; Wicke, B. G.
1977-01-01
The first study of the low-energy electron-impact excitation of low-lying electronic transitions in the HCN molecule is reported. Measurements were made at incident electron energies of 11.6 and 21.6 eV in the energy-loss range of 3-10 eV, and at scattering angles of 20-130 deg. Inelastic scattering spectra were placed on the absolute cross-section scale by determining first the ratio of inelastic-to-elastic scattering cross sections, and then separately measuring the absolute elastic scattering cross section. Several new electronic transitions are observed which are intrinsically overlapped in the molecule itself. Assignments of these electronic transitions are suggested. These assignments are based on present spectroscopic and cross-sections measurements, high-energy electron scattering spectra, optical absorption spectra, and ab initio molecular orbital calculations.
Stability of singlet and triplet trions in carbon nanotubes
DEFF Research Database (Denmark)
Rønnow, Troels Frimodt; Pedersen, Thomas Garm; Cornean, Horia
2009-01-01
We investigate singlet and triplet trion states in semiconducting carbon nanotubes using a one-dimensional model. It is concluded that singlet trion states in bind up to 13.5% stronger than exciton states, and that they lower the optical transition energy with up to 50% of the tight binding band ...
Schmidt, Reinhard
2006-05-11
A large set of literature kinetic data on triplet (T(1)) sensitization of singlet oxygen by two series of biphenyl and naphthalene sensitizers in solvents of strongly different polarity has been analyzed. The rate constants and the efficiencies of singlet oxygen formation are quantitatively reproduced by a model that assumes the competition of a non-charge transfer (nCT) and a CT deactivation channel. nCT deactivation occurs from a fully established spin-statistical equilibrium of (1)(T(1)(3)Sigma) and (3)(T(1)(3)Sigma) encounter complexes by internal conversion (IC) to lower excited complexes that dissociate to yield O(2)((1)Sigma(g)(+)), O(2)((1)Delta(g)), and O(2)((3)Sigma(g)(-)). IC of (1,3)(T(1)(3)Sigma) encounter complexes is controlled by an energy gap law that is generally valid for the transfer of electronic energy to and from O(2). (1,3)(T(1)(3)Sigma) nCT complexes form in competition to IC (1)(T(1)(3)Sigma) and (3)(T(1)(3)Sigma) exciplexes if CT interactions between T(1) and O(2) are important. The rate constants of exciplex formation depend via a Marcus type parabolic model on the corresponding free energy change DeltaG(CT), which varies with sensitizer triplet energy, oxidation potential, and solvent polarity. O(2)((1)Sigma(g)(+)), O(2)((1)Delta(g)), and O(2)((3)Sigma(g)(-)) are formed in the product ratio (1/6):(1/12):(3/4) in the CT deactivation channel. The balance between nCT and CT deactivation is described by the relative contribution p(CT) of CT induced deactivation calculated for a sensitizer of known triplet energy from its quenching rate constant. It is shown how the change of p(CT) influences the quenching rate constant and the efficiency of singlet oxygen formation in both series of sensitizers. p(CT) is sensitive to differences of solvent polarity and varies for the biphenyls and the naphthalenes as sigmoidal with DeltaG(CT). This quantitative model represents a realistic and general mechanism for the quenching of pipi triplet states by O
Theoretical spectroscopy study of the low-lying electronic states of UX and UX+, X = F and Cl
Bross, David H.; Peterson, Kirk A.
2015-11-01
Spectroscopic constants (Te, re, B0, ωe, and ωexe) have been calculated for the low-lying electronic states of UF, UF+, UCl, and UCl+ using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess Hamiltonians for the U atom. Spin orbit (SO) effects were included a posteriori using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component methods for U+ and UF+. Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω = 9/2 ground states. The first excited state of UCl was calculated to be an Ω = 7/2 state at 78 cm-1 as opposed to the same state at 435 cm-1 in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise, UF+ and UCl+ both have Ω = 4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states was energetically closer together in UCl+ than in UF+, ranging up to 776 cm-1 in UF+ and only 438 cm-1 in UCl+. As in previous studies, the final PP-based SO-CASPT2 results for UF+ and UF agree well with experiment and are expected to be predictive for UCl and UCl+, which are reported here for the first time.
Theoretical spectroscopy study of the low-lying electronic states of UX and UX(+), X = F and Cl.
Bross, David H; Peterson, Kirk A
2015-11-14
Spectroscopic constants (Te, re, B0, ωe, and ωexe) have been calculated for the low-lying electronic states of UF, UF(+), UCl, and UCl(+) using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess Hamiltonians for the U atom. Spin orbit (SO) effects were included a posteriori using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component methods for U(+) and UF(+). Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω = 9/2 ground states. The first excited state of UCl was calculated to be an Ω = 7/2 state at 78 cm(-1) as opposed to the same state at 435 cm(-1) in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise, UF(+) and UCl(+) both have Ω = 4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states was energetically closer together in UCl(+) than in UF(+), ranging up to 776 cm(-1) in UF(+) and only 438 cm(-1) in UCl(+). As in previous studies, the final PP-based SO-CASPT2 results for UF(+) and UF agree well with experiment and are expected to be predictive for UCl and UCl(+), which are reported here for the first time.
Theoretical spectroscopy study of the low-lying electronic states of UX and UX{sup +}, X = F and Cl
Energy Technology Data Exchange (ETDEWEB)
Bross, David H.; Peterson, Kirk A., E-mail: kipeters@wsu.edu [Department of Chemistry, Washington State University, Pullman, Washington 99164-4630 (United States)
2015-11-14
Spectroscopic constants (T{sub e}, r{sub e}, B{sub 0}, ω{sub e}, and ω{sub e}x{sub e}) have been calculated for the low-lying electronic states of UF, UF{sup +}, UCl, and UCl{sup +} using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess Hamiltonians for the U atom. Spin orbit (SO) effects were included a posteriori using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component methods for U{sup +} and UF{sup +}. Complete basis set (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω = 9/2 ground states. The first excited state of UCl was calculated to be an Ω = 7/2 state at 78 cm{sup −1} as opposed to the same state at 435 cm{sup −1} in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise, UF{sup +} and UCl{sup +} both have Ω = 4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states was energetically closer together in UCl{sup +} than in UF{sup +}, ranging up to 776 cm{sup −1} in UF{sup +} and only 438 cm{sup −1} in UCl{sup +}. As in previous studies, the final PP-based SO-CASPT2 results for UF{sup +} and UF agree well with experiment and are expected to be predictive for UCl and UCl{sup +}, which are reported here for the first time.
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
Hasanayn, Faraj; Markarian, Marie-Zabel; Al-Rifai, Rasha
2004-06-14
DFT methods have been used to investigate the dependence of the geometry and energy order of the low energy states of [d(4)-eta(5)-CpMo(CO)(2)X] 16-electron complexes on X (X = halogen, CN, H and CH(3)). The calculations use a double-zeta plus polarization valence basis set on all atoms and utilize relativistic ECPs on Mo and the heavier halogens. In every case two singlet and two triplet electronic states have been considered and minimized at the B3LYP level. For X = Cl, additional calculations were carried out at the BPW91, CCSD(T), and CASSCF levels. In the C(s) point group, the singlet states are from the (1a')(2)(1a'')(2) and (1a')(2)(2a')(2) configurations of the valence d(4) electrons of the metal, and are denoted (1)A'-a and (1)A'-b, respectively. The triplet species are for the lowest (3)A'' and (3)A' states from the (1a')(2)(2a')(1)(1a'')(1) and (1a'')(2)(1a')(1)(2a')(1) d(4) configurations. For all substituents, the geometry of both the singlet and triplet states is found to distort substantially from the uniform 3-leg piano-stool structural motif, a behavior that can be related to Jahn-Teller effects. When X is a halogen or a methyl, (1)A'-b is predicted to be lower than (1)A'-a, while the reverse order of these two singlet states is calculated for X = H and CN. For all substituents (3)A' is substantially higher than (3)A''. In turn, the energy of (3)A'' is calculated to be comparable to the lower singlet state of each complex. Attempts are made to rationalize some of these results using qualitative MO theory.
Koseki, Shiro; Matsushita, Takeshi; Gordon, Mark S
2006-02-23
The dissociation curves of low-lying spin-mixed states in monohydrides of groups 6 and 7 were calculated by using an effective core potential (ECP) approach. This approach is based on the multiconfiguration self-consistent field (MCSCF) method, followed by first-order configuration interaction (FOCI) calculations, in which the method employs an ECP basis set proposed by Stevens and co-workers (SBKJC) augmented by a set of polarization functions. Spin-orbit coupling (SOC) effects are estimated within the one-electron approximation by using effective nuclear charges, since SOC splittings obtained with the full Breit-Pauli Hamitonian are underestimated when ECP basis sets are used. The ground states of group 6 hydrides have Omega = (1)/(2)(X(6)Sigma(+)(1/2)), where Omega is the z component of the total angular momentum quantum number. Although the ground states of group 7 hydrides have Omega = 0(+), their main adiabatic components are different; the ground state in MnH originates from the lowest (7)Sigma(+), while in TcH and ReH the main component of the ground state is the lowest (5)Sigma(+). The present paper reports a comprehensive set of theoretical results including the dissociation energies, equilibrium distances, electronic transition energies, harmonic frequencies, anharmonicities, and rotational constants for several low-lying spin-mixed states in these hydrides. Transition dipole moments were also computed among the spin-mixed states and large peak positions of electronic transitions are suggested theoretically for these hydrides. The periodic trends of physical properties of metal hydrides are discussed, based on the results reported in this and other recent studies.
Zipf, E. C.; Gorman, M. R.
1980-01-01
Results of a study of the electron-impact excitation of the b 1 pi u state of N2, one of the singlet states thought to be excited by precipitating electrons in the auroral zones, and of its predissociation and radiative relaxation through the emission of the Birge-Hopfield band system (b 1 pi u - X 1 Sigma g +) are presented. A collimated electron beam was passed through N2 gas producing a variety of atomic states through dissociative excitation, and the radiation resulting from relaxation of these states was observed by VUV and visible-IR monochromators. Absolute emission cross sections for 11 Birge-Hopfield bands are obtained for energies from threshold to 500 eV, and used to calculate the absolute transition probabilities for BH(1, v-prime) bands and the variation of the electric dipole moment with internuclear distance. With the exception of the v-prime equals 1, 5 and 6 vibrational levels, all b 1 pi u levels are found to predissociate with a specific predissociation branching ratio greater than 0.99, representing a major source of nitrogen atoms.
Institute of Scientific and Technical Information of China (English)
Yao Jiang-Ming; Meng Jie; D. Pena Arteaga; P. Ring
2008-01-01
A full three-dimensional angular momentum projection on top of a triaxial relativistic mean-field calculation is implemented for the first time. The underlying Lagrangian is a point coupling model and pairing correlations are taken into account by a monopole force. This method is applied for the low-lying excited states in 24Mg. Good agreement with the experimental data is found for the ground state properties. A minimum in the potential energy surface for the 2+ state, with β≈ 0.55, γ≈ 10°, is used as the basis to investigate the rotational energyspectrum as well as the corresponding B(E2) transition probabilities as compared to the available data.
The development of efficient two-photon singlet oxygen sensitizers
DEFF Research Database (Denmark)
Nielsen, Christian Benedikt
The development of efficient two-photon singlet oxygen sensitizers is addressed focusing on organic synthesis. Photophysical measurements were carried out on new lipophilic molecules, where two-photon absorption cross sections and singlet oxygen quantumyields were measured. Design principles...... for making efficient two-photon singlet oxygen sensitizers were then constructed from these results. Charge-transfer in the excited state of the prepared molecules was shown to play a pivotal role in the generationof singlet oxygen. This was established through studies of substituent effects on both...... the singlet oxygen yield and the two-photon absorption cross section, where it was revealed that a careful balancing of the amount of charge transfer present in theexcited state of the sensitizer is necessary to obtain both a high singlet oxygen quantum yield and a high two-photon cross section. An increasing...
Energy Technology Data Exchange (ETDEWEB)
Kim, Sang Kyu [Univ. of California, Berkeley, CA (United States)
1993-05-01
The rotational distributions of CO products from the dissociation of ketene at photolysis energies 10 cm^{-1} below, 56, 110, 200, 325, 425, 1,107, 1,435, 1,720, and 2,500 cm^{-1} above the singlet threshold, are measured in a supersonic free jet of ketene. The CO(v'' = 0) rotational distributions at 56, 110, 200, 325, and 425 cm^{-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'' = 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^{-1} below the singlet threshold. At 2,500 cm^{-1} excess energy, the CO(v'' = 1) rotational distribution is obtained, and the ratio of CO(v'' = 1) to CO(v'' = 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_{2}CO) and deuterated ketene (CD_{2}CO) have been measured at the threshold for the production of the CH(D)_{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.
The low-lying 2-sigma-minus states of OH
Van Dishoeck, E. F.; Langhoff, S. R.; Dalgarno, A.
1983-01-01
The configuration-interaction method is used to determine the electronic wave functions of the two lowest 2-sigma-minus states of OH using four different atomic orbital basis sets. Potential energy curves, transition moments, oscillator strengths, and photodissociation cross sections are obtained. Electronic transition dipole moments connecting the excited 1 2-sigma-minus and 2(D)2-sigma-minus states with each other and with the ground chi-2-pi state are presented as functions of internuclear distance. The theoretical absorption oscillator strengths for the D-2-sigma-minus(v prime = 0) from chi-2-pi(v double prime = 0) transition are in good agreement with the empirical value derived from astronomical measurement. The photodissociation cross sections for absorption from the v prime = 0, 1, and 2 levels of the ground state into the continuum of the 1 2-sigma-minus state are calculated, and the interstellar and cometary photodissociation rates are derived.
Low-lying quasibound rovibrational states of H2 16O**
Szidarovszky, Tamás; Császár, Attila G.
2013-08-01
A complex coordinate scaling (CCS) method is described allowing the quantum chemical computation of quasibound (also called resonance or metastable) rovibrational states of strongly bound triatomic molecules. The molecule chosen to test the method is H2 16O, for which an accurate global potential energy surface, a previous computation of a few resonance states via the complex absorbing potential (CAP) method, and some Feshbach (J = 0, where J is the quantum number characterising overall rotations of the molecule) and shape (J ≠ 0) resonances measured via a state-selective, triple-resonance technique are all available. Characterisation of the computed resonance states is performed via probability density plots based on CCS rovibrational wavefunctions. Such plots provide useful details about the physical nature of the resonance states. Based on the computations and the resonance plots, the following useful facts about the resonance states investigated are obtained: (a) Feshbach resonances are formed by accumulation of a large amount of energy in either the non-dissociative bending or symmetric streching modes, excitations by more than five quanta are not uncommon; (b) there are several resonance states with low and medium bending excitation, the latter are different from the states observed somewhat below dissociation by the same triple-resonance technique; (c) several types of dissociation bahavior can be identified, varying greatly among the states; (d) several pairs of J = 0 and J = 1 Feshbach resonance states can be identified which differ by rigid-rotor type energies; and (e) the lifetimes of the assigned J = 1 rovibrational Feshbach resonances are considerably longer than the lifetimes of their J = 0 vibrational counterparts.
Lifetimes and collectivity of low-lying states in 115Sn
Lobach, Yu. N.; Käubler, L.; Schwengner, R.; Pasternak, A. A.
1999-04-01
The lifetimes of excited states in 115Sn have been measured using the Doppler shift attenuation method in the reaction 113Cd(α,2nγ) at Eα=27.2 MeV. Lifetimes were obtained for 18 states and lifetime limits for 6 states with Ex<=4 MeV and J<=23/2. The experimentally obtained B(σL) values for transitions deexciting positive-parity states are compared with calculations in the framework of the Bardeen-Cooper-Schrieffer quasiparticle model and the interacting boson fermion model, whereas the values for transitions between negative-parity states are discussed qualitatively within a core-particle coupling picture. The value of B(E2)=3.5(11) Weisskopf units (W.u.) for the transition linking the 19/2- state of the intruder νh11/2π2p2h band to the 15/2- state of the νh11/2⊗2+1 multiplet strongly supports the configuration νh11/2π(g-29/2g27/2) ascribed to this band.
Observation of a low-lying neutron-unbound state in 19C
Thoennessen, M; Badger, N S; Baumann, T; Bazin, D; Bennett, M; Brown, J; Christian, G; DeYoung, P A; Finck, J E; Gardner, M; Hook, E A; Luther, B; Meyer, D A; Mosby, M; Rogers, W F; Smith, J K; Spyrou, A; Strongman, M J
2013-01-01
Proton removal reactions from a secondary 22N beam were utilized to populate unbound states in neutron-rich carbon isotopes. Neutrons were measured with the Modular Neutron Array (MoNA) in coincidence with carbon fragments. A resonance with a decay energy of 76(14) keV was observed in the system 18C+n corresponding to a state in 19C at an excitation energy of 653(95)keV. This resonance could correspond to the first 5/2+ state which was recently speculated to be unbound in order to describe 1n and 2n removal cross section measurements from 20C.
Alpha clustering in $^{28}$Si probed through the identification of high-lying $0^+$ states
Adsley, P; Cseh, J; Dimitriova, S S; Brummer, J W; Li, K C W; Marin-Lambarri, D J; Lukyanov, K; Kheswa, N Y; Neveling, R; Papka, P; Pellegri, L; Pesudo, V; Pool, L C; Riczu, G; Smit, F D; van Zyl, J J; Zemlyanaya, E
2016-01-01
Aspects of nuclear structure in alpha-conjugate nuclei have long been associated with alpha clustering, including the existence of superdeformed bands. In this paper, an alpha-particle inelastic scattering experiment investigating the location of $0^+$ states in $^{28}$Si is reported in an attempt to locate possible cluster states. The results are compared to a semi-microscopic model which shows good agreement with the data, and supports the assignment of a newly discovered $0^+$ state as the band-head of a previously observed superdeformed band in $^{28}$Si
Chen, Wang; Kawaguchi, Kentarou; Bernath, Peter F; Tang, Jian
2015-02-14
6229 lines of the Ballik-Ramsay system (b(3)Σg (-)-a(3)Πu) and the Phillips system (A(1)Πu-X(1)Σg (+)) of C2 up to v = 8 and J = 76, which were taken from the literature or assigned in the present work, were analyzed simultaneously by least-squares fitting with 82 Dunham-like molecular parameters and spin-orbit interaction constants between the b(3)Σg (-) and X(1)Σg (+) states with a standard deviation of 0.0037 cm(-1) for the whole data set. As a result of the deperturbation analysis, the spin-orbit interaction constant AbX was determined as 6.333(7) cm(-1) and the energy difference between the X(1)Σg (+) and a(3)Πu states was determined as 720.008(2) cm(-1) for the potential minima or 613.650(3) cm(-1) for the v = 0 levels with Merer and Brown's N(2) Hamiltonian for (3)Π states, which is about 3.3 cm(-1) larger than the previously determined value. Due to this sizable change, a new energy-level crossing was found at J = 2 for v = 3 (F1) of b(3)Σg (-) state and v = 6 of X(1)Σg (+) state, where the strong interaction causes a nearly complete mixing of the wave functions of the b(3)Σg (-) and X(1)Σg (+) states and the forbidden transitions become observable. Using the predictions of our deperturbation analysis, we were able to identify 16 forbidden transitions between the singlet and triplet states at the predicted frequencies with the expected intensities, which verifies our value for the energy difference between the X(1)Σg (+) and a(3)Πu states.
Lifetime measurements of high-lying short lived states in {sup 69}As
Energy Technology Data Exchange (ETDEWEB)
Matejska-Minda, M.; Bednarczyk, P.; Fornal, B.; Ciemala, M.; Kmiecik, M.; Krzysiek, M.; Maj, A.; Meczynski, W.; Myalski, S.; Styczen, J.; Zieblinski, M.; Angelis, G. de; Huyuk, T.; Michelagnoli, C.; Sahin, E.; Aydin, S.; Farnea, E.; Menegazzo, R.; Recchia, F.; Ur, C. A. [Institute of Nuclear Physics, Polish Academy of Sciences, Krakow (Poland); INFN, Laboratori Nazionali di Legnaro, Legnaro (Italy); Dipartimento di Fisica e INFN Padova (Italy); Dipartimento di Fisica e INFN Milano (Italy); Heavy Ion Laboratory, University of Warsaw (Poland); University of York (United Kingdom); and others
2012-10-20
Lifetimes of high-spin states in {sup 69}As have been measured using Doppler shift attenuation technique with the GASP and RFD setup. The determined transition probabilities indicate large deformation associated with some rotational bands in this nucleus.
Understanding close-lying exotic charmonia states within QCD sum rules
Martínez Torres, A.; Khemchandani, K. P.; Dias, J. M.; Navarra, F. S.; Nielsen, M.
2017-10-01
Motivated by the experimental findings of some new exotic states decaying into channels like J / ψϕ, we investigate the formation of resonances/bound states in the Ds* Dbars* system using QCD sum rules. To do this we start with a current of the type vector times vector and use spin projectors to separate the spin 0, 1 and 2 contributions to the correlation function. We find three states with isospin 0, nearly spin degenerate, with a mass around 4.1 GeV. We have also investigated the decay of these states to J / ψϕ and provide the corresponding partial widths. Such information should be useful for experimental studies in future.
Mizuyama, Kazuhito
2013-01-01
The proton inelastic scattering of $^{24}$O($p,p'$) at 62 MeV/nucleon is described by a self-consistent microscopic calculation with the continuum particle-vibration coupling (cPVC) method. The SLy5, SkM*, and SGII parameters are adopted as an effective nucleon-nucleon interaction. For all the parameters, the cPVC calculation reproduces very well the first peak at 4.65 MeV in the $^{24}$O excitation energy spectrum as well as its angular distribution. The role of the cPVC self-energy strongly depends on the effective interactions. The higher-lying strength around 7.3 MeV is suggested to be a superposition of the $3^-$ and $4^+$ states by the results with SLy5 and SGII, whereas the SkM* calculation indicates it is a pure $3^-$ state. This difference gives a rather strong interaction dependence of the angular distribution corresponding to the higher-lying strength.
Three-body structure of low-lying {sup 18}Ne states
Energy Technology Data Exchange (ETDEWEB)
Lay, J.A. [Universidad de Sevilla, Departamento de Fisica Atomica, Molecular y Nuclear, Sevilla (Spain); Fedorov, D.V.; Jensen, A.S. [Aarhus University, Department of Physics and Astronomy, Aarhus C (Denmark); Garrido, E.; Romero-Redondo, C. [CSIC, Instituto de Estructura de la Materia, Madrid (Spain)
2010-05-15
We investigate to what extent {sup 18}Ne can be descibed as a three-body system made of an inert {sup 16}O core and two protons. We compare to experimental data and occasionally to shell model results. We obtain three-body wave functions with the hyperspherical adiabatic expansion method. We study the spectrum of {sup 18}Ne, the structure of the different states and the predominant transition strengths. Two 0{sup +}, two 2{sup +}, and one 4{sup +} bound states are found where they are all known experimentally. Also one 3{sup +} close to threshold is found and several negative-parity states, 1{sup -}, 3{sup -}, 0{sup -}, 2{sup -}, most of them bound with respect to the {sup 16}O excited 3{sup -} state. The structures are extracted as partial-wave components, as spatial sizes of matter and charge, and as probability distributions. Electromagnetic decay rates are calculated for these states. The dominating decay mode for the bound states is E2 and occasionally also M1. (orig.)
Spectroscopic Parameter and Molecular Constant Investigations on Low-Lying States of BeF Radical
Directory of Open Access Journals (Sweden)
Jin Feng Sun
2012-02-01
Full Text Available The potential energy curves (PECs of X2Σ+, A2Πr and B2Σ+ states of BeF radical have been investigated using the complete active space self-consistent-field (CASSCF method, followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI approach at the correlation-consistent basis sets, cc-pV5Z for Be and aug-cc-pV6Z for F. Based on the PECs of X2Σ+, A2Πr and B2Σ+ states, the spectroscopic parameters (De, Re, ωe, ωeχe, αe and Be have also been determined in the present work. With the PECs determined at the present level of theory, vibrational states have been predicted for each state when the rotational quantum number J equals zero (J = 0. The vibrational levels, inertial rotation and centrifugal distortion constants are determined for the three states, and the classical turning points are also calculated for the X2Σ+ state. Compared with the available experiments and other theories, it can be seen that the present spectroscopic parameter and molecular constant results are more fully in agreement with the experimental findings.
Indian Academy of Sciences (India)
Anjan Chattopadhyay
2010-03-01
Configuration interaction studies of H2F+ and H2Cl+ ions, using 6-311G (3, 3) basis sets, have revealed several interesting differences in their spectral behaviour. Both of them are having bent ground state (1A1) equilibrium geometries, but there is a huge difference (∼ 1.93 eV) between their energy barrier to linearity. Their first two excited states are found to be linear 3u and 1u states, correlating to 3B1/3A1 and 1B1/1A1 Renner-Teller pairs, respectively, in the C2v symmetry. Considering only the allowed singlet-singlet transitions at the ground state equilibrium geometry, the lowest energy transitions found to have transition moment values of 0.65 D and 0.48 D for H2F+and H2Cl+, respectively, appearing in the far UV region. Conical intersections take place during the symmetrical stretching of two H-Cl bonds in the chloronium ion for the first two pairs of excited states (11A2/11B1 and 11A2/11B1) in the C2v symmetry. This intersection may initiate pre-dissociation from the upper bound adiabatic 1A″ state to the lower repulsive 1A" state in the Cs symmetry. Fluoronium ion is expected to dissociate via a single electronic state due to the absence of such intersection.
The structure of low-lying states in ${}^{140}$Sm studied by Coulomb excitation
Klintefjord, M.; Görgen, A.; Bauer, C.; Bello Garrote, F.L.; Bönig, S.; Bounthong, B.; Damyanova, A.; Delaroche, J.P.; Fedosseev, V.; Fink, D.A.; Giacoppo, F.; Girod, M.; Hoff, P.; Imai, N.; Korten, W.; Larsen, A.C.; Libert, J.; Lutter, R.; Marsh, B.A.; Molkanov, P.L.; Naïdja, H.; Napiorkowski, P.; Nowacki, F.; Pakarinen, J.; Rapisarda, E.; Reiter, P.; Renstrøm, T.; Rothe, S.; Seliverstov, M.D.; Siebeck, B.; Siem, S.; Srebrny, J.; Stora, T.; Thöle, P.; Tornyi, T.G.; Tveten, G.M.; Van Duppen, P.; Vermeulen, M.J.; Voulot, D.; Warr, N.; Wenander, F.; De Witte, H.; Zielińska, M.
2016-05-02
The electromagnetic structure of $^{140}$Sm was studied in a low-energy Coulomb excitation experiment with a radioactive ion beam from the REX-ISOLDE facility at CERN. The $2^+$ and $4^+$ states of the ground-state band and a second $2^+$ state were populated by multi-step excitation. The analysis of the differential Coulomb excitation cross sections yielded reduced transition probabilities between all observed states and the spectroscopic quadrupole moment for the $2_1^+$ state. The experimental results are compared to large-scale shell model calculations and beyond-mean-field calculations based on the Gogny D1S interaction with a five-dimensional collective Hamiltonian formalism. Simpler geometric and algebraic models are also employed to interpret the experimental data. The results indicate that $^{140}$Sm shows considerable $\\gamma$ softness, but in contrast to earlier speculation no signs of shape coexistence at low excitation energy. This work sheds more light on the onset of deformation and collectivit...
Observation of a low-lying neutron-unbound state in {sup 19}C
Energy Technology Data Exchange (ETDEWEB)
Thoennessen, M., E-mail: thoennessen@nscl.msu.edu [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Mosby, S. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Badger, N.S. [Department of Physics, Rhodes College, Memphis, TN 38112 (United States); Baumann, T.; Bazin, D. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Bennett, M. [Department of Physics, Westmont College, Santa Barbara, CA 93108 (United States); Brown, J. [Department of Physics, Wabash College, Crawfordsville, IN 47933 (United States); Christian, G. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); DeYoung, P.A. [Department of Physics, Hope College, Holland, MI 49423 (United States); Finck, J.E. [Department of Physics, Central Michigan University, Mt. Pleasant, MI 48859 (United States); Gardner, M. [Department of Physics, Westmont College, Santa Barbara, CA 93108 (United States); Hook, E.A. [Department of Physics, Rhodes College, Memphis, TN 38112 (United States); Luther, B. [Department of Physics, Concordia College, Moorhead, MN 56562 (United States); Meyer, D.A. [Department of Physics, Rhodes College, Memphis, TN 38112 (United States); Mosby, M. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Rogers, W.F. [Department of Physics, Westmont College, Santa Barbara, CA 93108 (United States); and others
2013-08-21
Proton removal reactions from a secondary {sup 22}N beam were utilized to populate unbound states in neutron-rich carbon isotopes. Neutrons were measured with the Modular Neutron Array (MoNA) in coincidence with carbon fragments. A resonance with a decay energy of 76(14) keV was observed in the system {sup 18}C+n corresponding to a state in {sup 19}C at an excitation energy of 653(95) keV. This resonance could correspond to the first 5/2{sup +} state which was recently speculated to be unbound in order to describe 1n and 2n removal cross section measurements from {sup 20}C.
Energy of the low-lying bound S-states of exotic two-muon three-body systems
Khan, Md Abdul
2014-01-01
Energies of the low-lying bound S-states (L=0) of exotic three-body systems, consisting a nuclear core of charge +Ze (Z being atomic number of the core) and two negatively charged valence muons, have been calculated by hyperspherical harmonics expansion method (HHEM). The three-body Schr\\H{o}dinger equation is solved assuming purely Coulomb interaction among the binary pairs of the three-body systems X$^{Z+}\\mu^-\\mu^-$ for Z=1 to 54. Convergence pattern of the energies have been checked with respect to the increasing number of partial waves $K_{max}$. For available computer facilities, calculations are feasible up to $K_{max}=28$ partial waves, however, calculation for still higher partial waves have been achieved through an appropriate extrapolation scheme. The dependence of bound state energies has been checked against increasing nuclear charge Z and finally, the calculated energies have been compared with the ones of the literature.
The nature of singlet exciton fission in carotenoid aggregates.
Musser, Andrew J; Maiuri, Margherita; Brida, Daniele; Cerullo, Giulio; Friend, Richard H; Clark, Jenny
2015-04-22
Singlet exciton fission allows the fast and efficient generation of two spin triplet states from one photoexcited singlet. It has the potential to improve organic photovoltaics, enabling efficient coupling to the blue to ultraviolet region of the solar spectrum to capture the energy generally lost as waste heat. However, many questions remain about the underlying fission mechanism. The relation between intermolecular geometry and singlet fission rate and yield is poorly understood and remains one of the most significant barriers to the design of new singlet fission sensitizers. Here we explore the structure-property relationship and examine the mechanism of singlet fission in aggregates of astaxanthin, a small polyene. We isolate five distinct supramolecular structures of astaxanthin generated through self-assembly in solution. Each is capable of undergoing intermolecular singlet fission, with rates of triplet generation and annihilation that can be correlated with intermolecular coupling strength. In contrast with the conventional model of singlet fission in linear molecules, we demonstrate that no intermediate states are involved in the triplet formation: instead, singlet fission occurs directly from the initial 1B(u) photoexcited state on ultrafast time scales. This result demands a re-evaluation of current theories of polyene photophysics and highlights the robustness of carotenoid singlet fission.
Theoretical study of the low-lying bound states of O2
Partridge, Harry; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.
1991-01-01
It is demonstrated that a complete-active-space self-consistent-field (CASSCF) (2p)/MRCI + Q (multireference configuration interaction with a Davidson correction) description in a (13s8p6d 4f2g)/((5s4p3d 2f1g) atomic natural orbits (ANO) basis set supplemented with diffuse functions provides a quantitative description of the six lowest states of O2. The calculated potentials are within 0.05 eV (1.2 kilocal/mol) of accurate experimental results. The importance of substantially expanding the primitive basis set has been investigated, and it is demonstrated that such expansions yield insignificant improvement in the spectroscopic constants. Potential energy curves have also been reported for the weakly bound states of O2. The 5Pi(g) state is estimated to have a D(e) of 0.16 +/- 0.03 eV. The upper bound of D(e) is found to be sufficiently large that the importance of this state as a precursor for the formation of O2 (b 1Sigma(t)(+)) and O(1S) should be reconsidered.
Godunov, I. A.; Yakovlev, N. N.; Terentiev, R. V.; Maslov, D. V.; Bataev, V. A.; Abramenkov, A. V.
2016-11-01
The S1←S0 vibronic spectra of gas-phase absorption at room temperature and fluorescence excitation of jet-cooled cyclopropanecarboxaldehyde (CPCA, c-C3H5CHO)were obtained and analyzed. In addition, the quantum chemical calculation (CASPT2/cc-pVTZ)was carried out for CPCA in the ground (S0) and lowest excited singlet (S1) electronic states. As a result, it was proved that the S1←S0 electronic excitation of the CPCA conformers (syn and anti) causes (after geometrical relaxation) significant structural changes, namely, the carbonyl fragments become non-planar and the cyclopropyl groups rotate around the central C-C bond. As a consequence, the potential energy surface of CPCA in the S1 state has six minima, 1ab, 2ab, and 3ab, corresponding to three pairs of mirror symmetry conformers: a and b. It was shown that vibronic bands of experimental spectra can be assigned to the 2(S1)←syn(S0) electronic transition with the origin at 30,481 cm-1. A number of fundamental vibrational frequencies for the 2 conformer of CPCA were assigned. In addition, several inversional energy levels for the 2 conformer were found and the 2a↔2b potential function of inversion was determined. The experimental barrier to inversion and the equilibrium angle between the CH bond and the CCO plane were calculated as 570 cm-1 and 28°, respectively.
Wegner, Th; Küllig, C.; Meichsner, J.
2017-02-01
In this series of two papers, the E-H transition in a planar inductively coupled radio frequency discharge (13.56 MHz) in pure oxygen is studied using comprehensive plasma diagnostic methods. The electron density serves as the main plasma parameter to distinguish between the operation modes. The (effective) electron temperature, which is calculated from the electron energy distribution function and the difference between the floating and plasma potential, halves during the E-H transition. Furthermore, the pressure dependency of the RF sheath extension in the E-mode implies a collisional RF sheath for the considered total gas pressures. The gas temperature increases with the electron density during the E-H transition and doubles in the H-mode compared to the E-mode, whereas the molecular ground state density halves at the given total gas pressure. Moreover, the singlet molecular metastable density reaches 2% in the E-mode and 4% in the H-mode of the molecular ground state density. These measured plasma parameters can be used as input parameters for global rate equation calculations to analyze several elementary processes. Here, the ionization rate for the molecular oxygen ions is exemplarily determined and reveals, together with the optical excitation rate patterns, a change in electronegativity during the mode transition.
Lifetime measurement of the low lying yrast states in 189Pt
Chuang-Ye, He; Jin-Long, Wang; Yi-Heng, Wu; Yun, Zheng; Guang-Sheng, Li; Cong-Bo, Li; Shi-Peng, Hu; Hong-Wei, Li; Jia-Jian, Liu; Peng-Wei, Luo; Shun-He, Yao
2013-01-01
Lifetimes of the positive-parity yrast band in 189Pt were measured using the recoil distance Doppler-shift method. A HPGe detector array consisting of 13 detectors was used in conjunction with the plunger device in CIAE. Excited states of 189Pt were populated by the 176Yb (18O, 5n) 189Pt fusion-evaporation reaction at a beam energy 87 MeV. The lifetimes of two levels belonging to the yrast band are measured. The results show that the 17/2+ state in the yrast band has large Qt value, but it deceases quickly with spin increasing. It may be contributed from the shape driving effect of the quasi-neutron from the i13/2 oribital.
Energy Technology Data Exchange (ETDEWEB)
Liu Baochang [Department of Medical Physics and Applied Radiation Sciences, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4K1 (Canada); Farrell, Thomas J; Patterson, Michael S, E-mail: Baochang.Liu@jcc.hhsc.c, E-mail: Mike.Patterson@jcc.hhsc.c [Department of Medical Physics, Juravinski Cancer Centre, 699 Concession Street, Hamilton, Ontario L8V 5C2 (Canada)
2010-10-07
Singlet oxygen ({sup 1}O{sub 2}) direct dosimetry and photosensitizer fluorescence photobleaching are being investigated and applied as dosimetric tools during 5-aminolevulinic acid (ALA)-induced protophorphyrin IX (PpIX) photodynamic therapy (PDT) of normal skin and skin cancers. The correlations of photosensitizer fluorescence and singlet oxygen luminescence (SOL) emission signals to {sup 1}O{sub 2} distribution and cumulative {sup 1}O{sub 2} dose are difficult to interpret because of the temporal and spatial variations of three essential components (light fluence rate, photosensitizer concentration and oxygen concentration) in PDT. A one-dimensional model is proposed in this paper to simulate the dynamic process of ALA-PDT of normal human skin in order to investigate the time-resolved evolution of PpIX, ground-state oxygen ({sup 3}O{sub 2}) and {sup 1}O{sub 2} distributions. The model incorporates a simplified three-layer semi-infinite skin tissue, Monte Carlo simulations of excitation light fluence and both PpIX fluorescence and SOL emission signals reaching the skin surface, {sup 1}O{sub 2}-mediated photobleaching mechanism for updating PpIX, {sup 3}O{sub 2} and {sup 1}O{sub 2} distributions after the delivery of each light dose increment, ground-state oxygen supply by diffusion from the atmosphere and perfusion from blood vessels, a cumulative {sup 1}O{sub 2}-dependent threshold vascular response, and the initial non-uniform distribution of PpIX. The PpIX fluorescence simulated using this model is compared with clinical data reported by Cottrell et al (2008 Clin. Cancer Res. 14 4475-83) for a range of irradiances (10-150 mW cm{sup -2}). Except for the vascular response, one set of parameters is used to fit data at all irradiances. The time-resolved depth-dependent distributions of PpIX, {sup 3}O{sub 2} and {sup 1}O{sub 2} at representative irradiances are presented and discussed in this paper, as well as the PDT-induced vascular response at different depths
Energy Technology Data Exchange (ETDEWEB)
Gustavsson, Thomas [Laboratoire Francis Perrin, CEA/DSM/DRECAM/SPAM - CNRS URA 2453, CEA/Saclay, F-91191 Gif-sur-Yvette (France)], E-mail: thomas.gustavsson@cea.fr; Banyasz, Akos [Laboratoire Francis Perrin, CEA/DSM/DRECAM/SPAM - CNRS URA 2453, CEA/Saclay, F-91191 Gif-sur-Yvette (France); Sarkar, Nilmoni [Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, WB (India); Markovitsi, Dimitra [Laboratoire Francis Perrin, CEA/DSM/DRECAM/SPAM - CNRS URA 2453, CEA/Saclay, F-91191 Gif-sur-Yvette (France); Improta, Roberto [Dipartimento di Chimica, Universita Federico II, Complesso Universitario Monte S. Angelo, Via Cintia, I-80126 Napoli (Italy); Istituto Biostrutture e Bioimmagini/CNR, V. Mezzocannone 6 - 80134 Napoli (Italy)
2008-06-23
The excited state lifetimes of uracil, thymine and 5-fluorouracil have been measured using femtosecond UV fluorescence upconversion in various protic and aprotic polar solvents. The fastest decays are observed in acetonitrile and the slowest in aqueous solution while those observed in alcohols are intermediate. No direct correlation with macroscopic solvent parameters such as polarity or viscosity is found, but hydrogen bonding is one key factor affecting the fluorescence decay. It is proposed that the solvent modulates the relative energy of two close-lying electronically excited states, the bright {pi}{pi}* and the dark n{pi}* states. This relative energy gap controls the non-radiative relaxation of the {pi}{pi}* state through a conical intersection close to the Franck-Condon region competing with the ultrafast internal conversion to the ground state. In addition, an inverse isotope effect is observed in D{sub 2}O where the decays are faster than in H{sub 2}O.
Institute of Scientific and Technical Information of China (English)
LU Peng-Fei; YAN Lei; YU Zhong-Yuan; GAO Yu-Feng; GAO Tao
2013-01-01
In this paper,potential energy curves for the X1∑+,a3∏,a'3∑+,d3△,A1∏ and I1∑-states of CO have been calculated using complete active space self-consistent field and multi-reference configuration interaction methods.The calculations have been performed at 108 nuclear separations from 0.7 to 4.0 (A) by the aug-cc-PV5Z basis set.Spectroscopic constants for the six low-lying electronic states are found in good agreement with experimental data.The vibrational states of the X1∑+ and A1∏ states are also calculated,which are reliable and accurate by comparison with the experimental data and the other theoretical values.The transition dipole moment (TDM) shows that the TDM of the two states (X1∑+ → A1∏) are reduced strongly with increase of bond length.
Observation of a Novel Low-Lying Excited State in Zinc Complexes.
1985-01-22
Truesdell and G. A. Crosby * Prepared for Publication In The Journal of the American Chemical Society Washington State University Chemical Physics Program...spin signature has not yet been determined. 14 J J- I.F. ...r at.ion/___.. Ielt I, ty Codes Av-*l and/er This work supported in part by the Office of...REFERENCES (I) -Bray, R. G.; Ferguson, J.; Hawkins, C. J. Aust. J. Chem. 1969, 22, 2091. (2) Highland, R. G.; Crosby, G.A. Manuscript In preparation . (3
Mikhailov, Ivan A.; Tafur, Sergio; Masunov, Artëm E.
2008-01-01
The effect of static and dynamic electron correlation on the nature of excited states and state-to-state transition dipole moments is studied with a multideterminant wave function approach on the example of all-trans linear polyenes ( C4H6 , C6H8 , and C8H10 ). Symmetry-forbidden singlet nAg states were found to separate into three groups: purely single, mostly single, and mostly double excitations. The excited-state absorption spectrum is dominated by two bright transitions: 1Bu-2Ag and 1Bu-mAg , where mAg is the state, corresponding to two-electron excitation from the highest occupied to lowest unoccupied molecular orbital. The richness of the excited-state absorption spectra and strong mixing of the doubly excited determinants into lower- nAg states, reported previously at the complete active space self-consistent field level of theory, were found to be an artifact of the smaller active space, limited to π orbitals. When dynamic σ-π correlation is taken into account, single- and double-excited states become relatively well separated at least at the equilibrium geometry of the ground state. This electronic structure is closely reproduced within time-dependent density-functional theory (TD DFT), where double excitations appear in a second-order coupled electronic oscillator formalism and do not mix with the single excitations obtained within the linear response. An extension of TD DFT is proposed, where the Tamm-Dancoff approximation (TDA) is invoked after the linear response equations are solved (a posteriori TDA). The numerical performance of this extension is validated against multideterminant-wave-function and quadratic-response TD DFT results. It is recommended for use with a sum-over-states approach to predict the nonlinear optical properties of conjugated molecules.
Zhang, Xiaomei; Liu, Xiaoting; Liang, Guiying; Li, Rui; Xu, Haifeng; Yan, Bing
2016-01-01
The potential energy curves (PECs) of the 22 Λ-S states of the phosphorus monoiodide (PI) molecule have been calculated at the level of MRCI+Q method with correlation-consistent quadruple-ζ quality basis set. The spectroscopic constants of the bound states are determined, which well reproduce the available measurements. The metastable a1Δ state has been reported for the first time, which lies between the X3Σ- and b1Σ+ states and have much deeper well than the ground state. The R-dependent spin-orbit (SO) matrix elements are calculated with the full-electron Breit-Pauli operator. Based on the SO matrix elements, the perturbations that the 23Π state may suffer from are analyzed in detail. The SOC effect makes the original Λ-S states split into 51 Ω states. In the zero-field splitting of the ground state X3Σ-, the spin-spin coupling contribution (2.23 cm-1) is found to be much smaller compared to the spin-orbit coupling contribution (50 cm-1). The avoided crossings between the Ω states lead to much shallower potential wells and the change of dissociation relationships of the states. The Ω-state wavefunctions are analyzed depending on their Λ-S compositions, showing the strong interactions among several quasidegenerate Λ-S states of the same total SO symmetry. The transition properties including electric dipole (E1), magnetic dipole (M1), and electric quadrupole (E2) transition moments (TMs), the Franck-Condon factors, the transition probabilities and the radiative lifetimes are computed for the transitions between Ω components of a1Δ and b1Σ+ states and ground state. The transition probabilities induced by the E1, E2, and M1 transitions are evaluated. The E2 makes little effect on transition probabilities. In contrast, the E1 transition makes the main contribution to the transition probability and the M1 transition also brings the influence that cannot be neglected. Finally, the radiative lifetimes are determined with the transition moments including E
Ground and low-lying excited electronic states of graphene flakes: a density functional theory study
Energy Technology Data Exchange (ETDEWEB)
Tachikawa, Hiroto; Kawabata, Hiroshi, E-mail: hiroto@eng.hokudai.ac.jp [Division of Materials Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan)
2011-10-28
Structures and electronic states of graphene flakes (finite and small sized graphenes) have been investigated by means of the density functional theory method. Sizes of graphene flakes examined in this study were n = 7, 10, 14, 19, 29 and 44, where n is the number of benzene rings in the graphene flake. The excitation energies of graphene flakes decreased gradually as a function of the number of the ring (n). The orbitals of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) are localized in the edge region of the graphene flake. It was found that the edge region can react with a water molecule and H{sub 2}O is dissociated into OH radical and hydrogen atom (H) without an activation barrier. A lithium ion can bind strongly to the edge region. The ability of the edge region in the graphene flakes was discussed on the basis of theoretical results.
Rosado-Lausell, Sahid L.
2013-09-01
Inactivation of bacteriophage MS2 by reactive oxygen species (ROS) and triplet excited state of dissolved organic matter (3DOM*) produced by irradiation of natural and synthetic sensitizers with simulated sunlight of wavelengths greater than 320nm was investigated. Natural sensitizers included purified DOM isolates obtained from wastewater and river waters, and water samples collected from Singapore River, Stamford Canal, and Marina Bay Reservoir in Singapore. Linear correlations were found between MS2 inactivation rate constants (kobs) and the photo-induced reaction rate constants of 2,4,6-trimethylphenol (TMP), a probe compound shown to react mainly with 3DOM*. Linear correlations between MS2 kobs and singlet oxygen (1O2) concentrations were also found for both purified DOM isolates and natural water samples. These correlations, along with data from quenching experiments and experiments with synthetic sensitizers, Rose Bengal (RB), 3\\'-methoxyacetophenone (3\\'-MAP), and nitrite (NO2-), suggest that 1O2, 3DOM*, and hydroxyl radicals (•OH) could inactivate bacteriophage MS2. Linear correlations between MS2 kobs and Specific Ultraviolet Absorption determined at 254nm (SUVA254) were also found for both purified DOM isolates and natural samples. These results suggest the potential use of TMP as a chemical probe and SUVA254 as an indicator for virus inactivation in natural and purified DOM water samples. © 2013 Elsevier Ltd.
Energy Technology Data Exchange (ETDEWEB)
Ito, T. [Miyagi Midical Univ., Miyagi (Japan)
2000-01-01
Specification of the lowest excited singlet state (S{sub l}) of the butadiene which is the simplest {pi} electron conjugated system molecule has not sufficiently clarified at present. Recently, Andersson et al. found the weak light emission which was considered to be the S{sub 1} fluorescence in a near infrared region in a room temperature solution of {beta}- carotene (n=11), and specified the S{sub 1} level in 14,200{+-}500cm {sup -1}. And, Fujii et al. reported the S{sub 1} fluorescence of spheroidine (n=10). In very recent, Christensen et al. measured the comparatively clear fluorescence spectrum of carotenes n=5 to 11 separated by HPLC in EPA glass at 77K, and systematically examined the unique luminescence property observed in polyene. Christensen et al. issued the warning for the rough conventional method that the S{sub 1} level was estimated from the S{sub 1} fluorescence lifetime of the polyene molecule using the comprehensive energy gap law, because the ratio of quantum yield of the S{sub 1} and S{sub 2} fluorescence is different by the substituent type of the polyene end even if n is same. (NEDO)
Zurdo, J; Fernández-Cabrera, C; Ramírez, J M
1992-06-01
The apparent quantum yield of singlet-singlet spirilloxanthin-to-bacteriochlorophyll a energy transfer increases linearly with the residual spirilloxanthin content in Rhodospirillum rubrum membrane vesicles from which this carotenoid has been partially removed. Since it has been previously shown that carotenoid-carotenoid interaction is a linear function of the residual spirilloxanthin level in the major pigment-protein complex of those vesicles (Zurdo, J., R. M. Lozano, C. Fernandez-Cabrera, and J. M. Ramirez. 1991. Biochem. J. 274:881-884), it appears that such degenerate interaction enhances singlet energy transfer. Part of the enhancement may be explained if the energy donor is the spirilloxanthin 1Bu----1Ag (S2----S0) transition, because exciton coupling probably brings its energy closer to that of the Qx (S2----S0) transition of bacteriochlorophyll. In contrast, it seems that the possible stabilization of the spirilloxanthin 2Ag (S1) state would hardly improve energy transfer, because this hidden state probably lies below the S1 bacteriochlorophyll state. In any case, the stabilizing effects of carotenoid-carotenoid interactions seem insufficient to explain the enhancement of energy transfer. Direct or indirect effects of carotenoid dimerization on the three-dimensional structure of the pigment cluster appear to be required to account for such enhancement.
Directory of Open Access Journals (Sweden)
C. Romig
2015-05-01
Full Text Available The technique of self absorption has been applied for the first time to study the decay pattern of low-lying dipole states of 140Ce. In particular, ground-state transition widths Γ0 and branching ratios Γ0Γ to the ground state have been investigated in the energy domain of the pygmy dipole resonance. Relative self-absorption measurements allow for a model-independent determination of Γ0. Without the need to perform a full spectroscopy of all decay channels, also the branching ratio to the ground state can be determined. The experiment on 140Ce was conducted at the bremsstrahlung facility of the superconducting Darmstadt electron linear accelerator S-DALINAC. In total, the self-absorption and, thus, Γ0 were determined for 104 excited states of 140Ce. The obtained results are presented and discussed with respect to simulations of γ cascades using the DICEBOX code.
Study of the γ decay of high-lying states in 208Pb via inelastic scattering of 17O ions
Directory of Open Access Journals (Sweden)
Crespi F.C.L.
2012-12-01
Full Text Available High-lying states in 208Pb nucleus were populated via inelastic scattering of a 17O beam at bombarding energy of 20 MeV/u. Their subsequent gamma decay was measured with the detector system AGATA Demonstrator based on HPGe detectors, coupled to an array of large volume LaBr3:Ce scintillators. Preliminary results in comparison with (γ,γ′ data, for states in the 5–8 MeV energy interval, seem to indicate that in that region the states belong to two different groups one with a isoscalar character and the other with a isovector nature. This is similar to what was observed in other stable nuclei with (α,α′γ experiments. The multipolarity of the observed gamma transitions is determined with remarkable sensitivity thanks to angular distribution measurements. Data aiming at studying the neutron decay of the Giant Quadrupole Resonance in the 208Pb by the high resolution measurement of the following gamma decay are also presented in their preliminary form.
Energy Technology Data Exchange (ETDEWEB)
Liao, Pen-Nan [Technische Universitat Braunschweig (Germany); Pillai, Smitha [Arizona State Univ., Tempe, AZ (United States); Gust, Devens [Arizona State Univ., Tempe, AZ (United States); Moore, Thomas A. [Arizona State Univ., Tempe, AZ (United States); Moore, Ana L. [Arizona State Univ., Tempe, AZ (United States); Walla, Peter J. [Technische Universitat Braunschweig (Germany)
2011-03-22
Electronic interactions between the first excited states (S_{1}) of carotenoids (Car) of different conjugation lengths (8-11 double bonds) and phthalocyanines (Pc) in different Car-Pc dyad molecules were investigated by two-photon spectroscopy and compared with Car S_{1}-chlorophyll (Chl) interactions in photosynthetic light harvesting complexes (LHCs). The observation of Chl/Pc fluorescence after selective two-photon excitation of the Car S_{1} state allowed sensitive monitoring of the flow of energy between Car S_{1} and Pc or Chl. It is found that two-photon excitation excites to about 80% to 100% exclusively the carotenoid state Car S_{1} and that only a small fraction of direct tetrapyrrole two-photon excitation occurs. Amide-linked Car-Pc dyads in tetrahydrofuran demonstrate a molecular gear shift mechanism in that effective Car S_{1} → Pc energy transfer is observed in a dyad with 9 double bonds in the carotenoid, whereas in similar dyads with 11 double bonds in the carotenoid, the Pc fluorescence is strongly quenched by Pc → Car S_{1} energy transfer. In phenylamino-linked Car-Pc dyads in toluene extremely large electronic interactions between the Car S_{1} state and Pc were observed, particularly in the case of a dyad in which the carotenoid contained 10 double bonds. This observation together with previous findings in the same system provides strong evidence for excitonic Car S_{1}-Pc Q_{y} interactions. Very similar results were observed with photosynthetic LHC II complexes in the past, supporting an important role of such interactions in photosynthetic down-regulation.
Bondarev, S. L.; Tikhomirov, S. A.; Buganov, O. V.; Knyukshto, V. N.; Raichenok, T. F.
2017-03-01
The spectroscopic and photophysical properties of the biologically important plant antioxidant quercetin in organic solvents, polymer films of polyvinyl alcohol, and a buffer solution at pH 7.0 are studied by stationary luminescence and femtosecond laser spectroscopy at room temperature and 77 K. The large magnitude of the dipole moment of the quercetin molecule in the excited Franck-Condon state μ e FC = 52.8 C m indicates the dipolar nature of quercetin in this excited state. The transient induced absorption spectra S 1→ S n in all solvents are characterized by a short-wave band at λ abs max = 460 nm with exponential decay times in the range of 10.0-20.0 ps. In the entire spectral range at times of >100 ps, no residual induced absorption was observed that could be attributed to the triplet-triplet transitions T 1 → T k in quercetin. In polar solvents, two-band fluorescence was also recorded at room temperature, which is due to the luminescence of the initial enol form of quercetin ( 415 nm) and its keto form with a transferred proton (550 nm). The short-wave band is absent in nonpolar 2-methyltetrahydrofuran (2-MTHF). The spectra of fluorescence and fluorescence excitation exhibit a low dependence on the wavelength of excitation and detection, which may be related to the solvation and conformational changes in the quercetin molecule. Decreasing the temperature of a glassy-like freezing quercetin solution in ethanol and 2-MTHF to 77 K leads to a strong increase in the intensity (by a factor of 100) of both bands. The energy circuits for the proton transfer process are proposed depending on the polarity of the medium. The main channel for the exchange of electronic excitation energy in the quercetin molecule at room temperature is the internal conversion S 1 ⇝ S 0, induced by the state with a proton transfer.
Oxygen measurements to improve singlet oxygen dosimetry
Kim, Michele M.; Penjweini, Rozhin; Ong, Yi Hong; Finlay, Jarod C.; Zhu, Timothy C.
2017-02-01
Photodynamic therapy (PDT) involves interactions between the three main components of light fluence, photosensitizer concentration, and oxygenation. Currently, singlet oxygen explicit dosimetry (SOED) has focused on the first two of these components. The macroscopic model to calculate reacted singlet oxygen has previously involved a fixed initial ground state oxygen concentration. A phosphorescence-based oxygen probe was used to measure ground state oxygen concentration throughout treatments for mice bearing radioactively induced fibroscarcoma tumors. Photofrin-, BPD-, and HPPH-mediated PDT was performed on mice. Model-calculated oxygen and measured oxygen was compared to evaluate the macroscopic model as well as the photochemical parameters involved. Oxygen measurements at various depths were compared to calculated values. Furthermore, we explored the use of noninvasive diffuse correlation spectroscopy (DCS) to measure tumor blood flow changes in response to PDT to improve the model calculation of reacted singlet oxygen. Mice were monitored after treatment to see the effect of oxygenation on long-term recurrence-free survival as well as the efficacy of using reacted singlet oxygen as a predictive measure of outcome. Measurement of oxygenation during treatment helps to improve SOED as well as confirm the photochemical parameters involved in the macroscopic model. Use of DCS in predicting oxygenation changes was also investigated.
Benniston, Andrew C; Harriman, Anthony; Li, Peiyi; Patel, Pritesh V; Sams, Craig A
2008-01-01
The rate constant for triplet energy transfer (k(TET)) has been measured in fluid solution for a series of mixed-metal Ru-Os bis(2,2':6',2''-terpyridine) complexes built around a tethered biphenyl-based spacer group. The length of the tether controls the central torsion angle for the spacer, which can be varied systematically from 37 to 130 degrees . At low temperature, but still in fluid solution, the spacer adopts the lowest-energy conformation and k(TET) shows a clear correlation with the torsion angle. A similar relationship holds for the inverse quantum yield for emission from the Ru-terpy donor. Triplet energy transfer is more strongly activated at higher temperature and the kinetic data require analysis in terms of two separate processes. The more weakly activated step involves electron exchange from the first-excited triplet state on the Ru-terpy donor and the size of the activation barrier matches well with that calculated from spectroscopic properties. The pre-exponential factor derived for this process correlates remarkably well with the torsion angle and there is a large disparity in electronic coupling through pi and sigma orbitals on the spacer. The more strongly activated step is attributed to electron exchange from an upper-lying triplet state localized on the Ru-terpy donor. Here, the pre-exponential factor is larger but shows the same dependence on the geometry of the spacer. Strangely, the difference in coupling through pi and sigma orbitals is much less pronounced. Despite internal flexibility around the spacer, k(TET) shows a marked dependence on the torsion angle computed for the lowest-energy conformation.
DEFF Research Database (Denmark)
Haldrup, Martin Kristoffer; Harlang, Tobias; Christensen, Morten;
2011-01-01
Ground- and excited-state structures of the bimetallic, ligand-bridged compound Ir2(dimen)42+ are investigated in acetonitrile by means of time-resolved X-ray scattering. Following excitation by 2 ps laser pulses at 390 nm, analysis of difference scattering patterns obtained at eight different ti...... the ∼100 ps probe width down to the 10 ps regime by positioning the laser pump pulse at selected points in the X-ray probe pulse. This approach is used to investigate the structures of both the singlet and the triplet excited states of Ir2(dimen)42+....
Samala, Nagaprasad Reddy; Mahapatra, S.
2014-06-01
Polycyclic aromatic hydrocarbons (PAHs), in particular, their radical cation (PAH^+), have long been postulated to be the important molecular species in connection with the spectroscopic observations in the interstellar medium. Motivated by numerous important observations by stellar as well as laboratory spectroscopists, we undertook detailed quantum mechanical studies of the structure and dynamics of electronically excited PAH^+ in an attempt to establish possible synergism with the recorded data In this study, we focus on the quantum chemistry and dynamics of the doublet ground (X) and low-lying excited (A, B and C) electronic states of the radical cation of tetracene (Tn), pentacene (Pn), and hexacene (Hn) molecule. This study is aimed to unravel photostability, spectroscopy, and time-dependent dynamics of their excited electronic states. In order to proceed with the theoretical investigations, we construct suitable multistate and multimode Hamiltonian for these systems with the aid of extensive ab initio calculations of their electronic energy surfaces. The diabatic coupling surfaces are derived from the calculated adiabatic electronic energies. First principles nuclear dynamics calculations are then carried out employing the constructed Hamiltonians and with the aid of time-independent and time-dependent quantum mechanical methods. We compared our theoretical results with available photoelectron spectroscopy, zero kinetic energy photoelectron (ZEKE) spectroscopy and matrix isolation spectroscopy (MIS) results. A peak at 8650 Å in the B state spectrum of Tn^+ is in good agreement with the DIB at 8648 Å observed by Salama et al. Similarly in Pn^+, a peak at 8350 Å can be correlated to the DIB at 8321 Å observed by Salama et al. J. Zhang et al., J. Chem. Phys., 128,104301 (2008).; F. Salama, Origins of Life Evol. Biosphere, 28, 349 (1998).; F. Salama et al., Planet. Space Sci., 43, 1165 (1995).; F. Salama et al., Astrophys. J., 526, 265 (1999).; J
Panov, Maxim S; Voskresenska, Valentyna D; Ryazantsev, Mikhail N; Tarnovsky, Alexander N; Wilson, R Marshall
2013-12-26
The photochemistry of a new photoaffinity labeling (PAL) agent, 5-azido-2-(N,N-diethylamino)pyridine, was studied in aprotic and protic solvents using femtosecond-to-microsecond transient absorption and product analysis, in conjunction with ab initio multiconfigurational and multireference quantum chemical calculations. The excited singlet S1 state is spectroscopically dark, whereas photoexcitation to higher-lying singlet excited S2 and S3 states drives the photochemical reaction toward a barrierless ultrafast relaxation path via two conical intersections to S1, where N2 elimination leads to the formation of the closed-shell singlet nitrene. The singlet nitrene undergoes intersystem crossing (ISC) to the triplet nitrene in aprotic and protic solvents as well as protonation to form the nitrenium ion. The ISC rate constants in aprotic solvents increase with solvent polarity, displaying a "direct" gap effect, whereas an "inverse" gap effect is observed in protic solvents. Transient absorption actinometry experiments suggest that a solvent-dependent fraction from 20% to 50% of nitrenium ions is generated on a time scale of a few tens of picoseconds. The closed-shell singlet and triplet nitrene are separated by a small energy gap in protic solvents. As a result, the unreactive triplet state nitrene undergoes delayed, thermally activated reverse ISC to reform the reactive closed-shell singlet nitrene, which subsequently protonates, forming the remaining fraction of nitrenium ions. The product studies demonstrate that the resulting nitrenium ion stabilized by the electron-donating 4-amino group yields the final cross-linked product with high, almost quantitative efficiency. The enhanced PAL function of this new azide with respect to the widely applied 4-amino-3-nitrophenyl azide is discussed.
Mukund, Sheo; Yarlagadda, Suresh; Bhattacharyya, Soumen; Nakhate, S. G.
2014-01-01
Laser-induced dispersed fluorescence spectra of 58Ni12C molecules, produced in a free-jet apparatus, have been studied. A new low-lying Ω = 0+ state has been observed at Te = 5178 (6) cm-1. Based on previous ab initio calculations this state is plausibly assigned as 0+ spin-orbit component of the first excited 3 Π state. The term energies of vibrational levels up to v = 10 for X1Σ+ ground and v = 3 for Ω = 0+ states have been determined. The harmonic and anharmonic wavenumbers respectively equal to 833 (4) and 6.7 (13) cm-1 for Ω = 0+ state have been measured.
Lie groups and Lie algebras for physicists
Das, Ashok
2015-01-01
The book is intended for graduate students of theoretical physics (with a background in quantum mechanics) as well as researchers interested in applications of Lie group theory and Lie algebras in physics. The emphasis is on the inter-relations of representation theories of Lie groups and the corresponding Lie algebras.
Energy Technology Data Exchange (ETDEWEB)
Sandor, R.K.J.; Blok, H.P.; Harakeh, M.N. (Vrije Univ., Amsterdam (Netherlands). Natuurkundig Lab.); Garg, U. (Vrije Univ., Amsterdam (Netherlands). Natuurkundig Lab. Notre Dame Univ., IN (USA). Dept. of Physics); Jager, C.W. de; Vries, H. de (Nationaal Inst. voor Kernfysica en Hoge-Energiefysica (NIKHEF), Amsterdam (Netherlands). Sectie K); Ponomarev, V.Yu.; Vdovin, A.I. (Joint Inst. for Nuclear Research, Dubna (USSR). Lab. of Theoretical Physics)
1989-12-21
The low-lying quadrupole states in {sup 142}Nd were investigated by inelastic electron scattering. The momentum transfer range covered was 0.5-2.8 fm{sup -1}. The extracted transition charge densities indicate quite different characters for these states. On the basis of a quasiparticle-phonon nuclear model calculation this difference can be understood as arising from an interplay between collective and single-particle aspects. (orig.).
Singlet fission: Towards efficient solar cells
Energy Technology Data Exchange (ETDEWEB)
Havlas, Zdeněk; Wen, Jin [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic); Michl, Josef [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215 (United States); Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 16610 Prague 6 (Czech Republic)
2015-12-31
Singlet fission (SF) offers an opportunity to improve solar cell efficiency, but its practical use is hindered by the limited number of known efficient materials, limited knowledge of SF mechanism, mainly the relation between the dimer structure and SF efficiency and diffusion of the triplet states allowing injection of electrons into the solar cell semiconductor band. Here we report on our attempt to design new classes of chromophores and to study the relation between the structure and SF efficiency.
Optical detection of singlet oxygen from single cells
DEFF Research Database (Denmark)
Snyder, John; Skovsen, Esben; Lambert, John D. C.;
2006-01-01
The lowest excited electronic state of molecular oxygen, singlet molecular oxygen, O2(a 1g), is a reactive species involved in many chemical and biological processes. To better understand the roles played by singlet oxygen in biological systems, particularly at the sub-cellular level, optical too...... for mechanistic studies of intra- and inter-cellular signaling and events that ultimately lead to photo-induced cell death....
Singlet Fission in Rubrene Derivatives: Impact of Molecular Packing
Sutton, Christopher
2017-03-13
We examine the properties of six recently synthesized rubrene derivatives (with substitutions on the side phenyl rings) that show vastly different crystal structures. In order to understand how packing in the solid state affects the excited states and couplings relevant for singlet fission, the lowest excited singlet (S), triplet (T), multiexciton (TT), and charge-transfer (CT) states of the rubrene derivatives are compared to known singlet fission materials [tetracene, pentacene, 5,12-diphenyltetracene (DPT), and rubrene itself]. While a small difference of less than 0.2 eV is calculated for the S and TT energies, a range of 0.50 to 1.2 eV in the CT energies and nearly 3 orders of magnitude in the electronic couplings are computed for the rubrene derivatives in their crystalline packings, which strongly affects the role of the CT state in facilitating SF. To rationalize experimental observations of singlet fission occurring in amorphous phases of rubrene, DPT, and tetracene, we use molecular dynamics (MD) simulations to assess the impact of molecular packing and orientations and to gain a better understanding of the parameters that control singlet fission in amorphous films compared to crystalline packings. The MD simulations point to a crystalline-like packing for thin films of tetracene; on the other hand, DPT, rubrene, and the rubrene derivatives all show various degrees of disorder with a number of sites that have larger electronic couplings than in the crystal, which can facilitate singlet fission in such thin films. Our analysis underlines the potential of these materials as promising candidates for singlet fission and helps understand how various structural motifs affect the critical parameters that control the ability of a system to undergo singlet fission.
Weak Lie symmetry and extended Lie algebra
Energy Technology Data Exchange (ETDEWEB)
Goenner, Hubert [Institute for Theoretical Physics, Friedrich-Hund-Platz 1, University of Goettingen, D-37077 Gottingen (Germany)
2013-04-15
The concept of weak Lie motion (weak Lie symmetry) is introduced. Applications given exhibit a reduction of the usual symmetry, e.g., in the case of the rotation group. In this context, a particular generalization of Lie algebras is found ('extended Lie algebras') which turns out to be an involutive distribution or a simple example for a tangent Lie algebroid. Riemannian and Lorentz metrics can be introduced on such an algebroid through an extended Cartan-Killing form. Transformation groups from non-relativistic mechanics and quantum mechanics lead to such tangent Lie algebroids and to Lorentz geometries constructed on them (1-dimensional gravitational fields).
Werner State Structure and Entanglement Classification
Directory of Open Access Journals (Sweden)
David W. Lyons
2012-01-01
Full Text Available We present applications of the representation theory of Lie groups to the analysis of structure and local unitary classification of Werner states, sometimes called the decoherence-free states, which are states of n quantum bits left unchanged by local transformations that are the same on each particle. We introduce a multiqubit generalization of the singlet state and a construction that assembles these qubits into Werner states.
Zhang, Chun Mei; Chen, Chao; Sun, Yan; Gou, Bing Cong; Shao, Bin
2015-04-01
The Rayleigh-Ritz variational method with multiconfiguration interaction wave functions is used to obtain the energies of high-lying multi-excited quartet states 1 s 22 s2 pnl and 1 s 22 p 2 nl 4Pe,o ( n ≥ 2) in B-like neon, including the mass polarization and relativistic corrections. The fine structure and hyperfine structure of the excited quartet states for this system are investigated. Configuration structures of the high-lying multi-excited series are further identified by relativistic corrections and fine structure splittings. The transition rates and wavelengths are also calculated. Calculated wavelengths include the quantum electrodynamic effects. The results are compared with other theoretical and experimental data in the literature.
Institute of Scientific and Technical Information of China (English)
白瑞蒲; 程宇; 李佳倩; 孟伟
2014-01-01
3-Lie algebras have close relationships with many important fields in mathemat-ics and mathematical physics. This article concerns 3-Lie algebras. The concepts of 3-Lie coalgebras and 3-Lie bialgebras are given. The structures of such categories of algebras and the relationships with 3-Lie algebras are studied. And the classification of 4-dimensional 3-Lie coalgebras and 3-dimensional 3-Lie bialgebras over an algebraically closed field of char-acteristic zero are provided.
Blue-light emission of Cu(I) complexes and singlet harvesting.
Czerwieniec, Rafał; Yu, Jiangbo; Yersin, Hartmut
2011-09-05
Strongly luminescent neutral copper(I) complexes of the type Cu(pop)(NN), with pop = bis(2-(diphenylphosphanyl)phenyl)ether and NN = bis(pyrazol-1-yl)borohydrate (pz(2)BH(2)), tetrakis(pyrazol-1-yl)borate (pz(4)B), or bis(pyrazol-1-yl)-biphenyl-borate (pz(2)Bph(2)), are readily accessible in reactions of Cu(acetonitrile)(4)(+) with equimolar amounts of the pop and NN ligands at ambient temperature. All products were characterized by means of single crystal X-ray diffractometry. The compounds exhibit very strong blue/white luminescence with emission quantum yields of up to 90%. Investigations of spectroscopic properties and the emission decay behavior in the temperature range between 1.6 K and ambient temperature allow us to assign the emitting electronic states. Below 100 K, the emission decay times are in the order of many hundreds of microseconds. Therefore, it is concluded that the emission stems from the lowest triplet state. This state is assigned to a metal-to-ligand charge-transfer state (3MLCT) involving Cu-3dand pop-π* orbitals. With temperature increase, the emission decay time is drastically reduced, e.g. to 13 μs [corrected] (Cu(pop)-(pz(2)Bph(2))), at ambient temperature. At this temperature, the complexes exhibit high emission quantum yields, as neat material or doped into poly(methyl methacrylate) (PMMA). This behavior is assigned to an efficient thermal population of a singlet state (being classified as (1)MLCT), which lies only 800 to 1300 cm(-1) above the triplet state, depending on the individual complex. Thus, the resulting emission at ambient temperature largely represents a fluorescence. For applications in OLEDs and LEECs, for example, this type of thermally activated delayed fluorescence (TADF) creates a new mechanism that allows to harvest both singlet and triplet excitons (excitations) in the lowest singlet state. This effect of singlet harvesting leads to drastically higher radiative rates than obtainable for emissions from triplet
Photoluminescence dynamics in singlet fission chromophore liquid melts
Piland, Geoffrey B.; Bardeen, Christopher J.
2017-02-01
The effect of high temperature melting on the photophysics of three prototypical singlet fission molecules is investigated. Time-resolved photoluminescence is used to look at the melt phase of the molecules tetracene, diphenylhexatriene and rubrene. Chemical decomposition of tetracene precluded any detailed measurements on this molecule. In the diphenylhexatriene melt, a rapid singlet state nonradiative relaxation process outcompetes singlet fission. In the rubrene melt, singlet fission occurs at a rate similar to that of the crystal, but the decay of the delayed fluorescence is much more rapid. The rapid decay of the delayed fluorescence suggests that either the triplet lifetime is shortened, or the fusion probability decreases, or that both factors are operative at higher temperatures.
Energy Technology Data Exchange (ETDEWEB)
Sandor, R.K.J.; Blok, H.P.; Harakeh, M.N. (Dept. of Physics and Astronomy, Vrije Univ., Amsterdam (Netherlands)); Garg, U. (Dept. of Physics and Astronomy, Vrije Univ., Amsterdam (Netherlands) Physics Dept., Univ. Notre Dame, IN (United States)); Jager, C.W. de; Vries, H. de (Nationaal Inst. voor Kernfysica en Hoge-Energie Fysica, Amsterdam (Netherlands)); Ponomarev, V.Yu.; Vdovin, A.I. (Lab. of Theoretical Physics, Joint Inst. for Nuclear Research Dubna, Moscow (USSR))
1991-12-30
The low-lying excited states in {sup 142}Nd were investigated by inelastic electron scattering. The momentum transfer range covered was 0.5-2.8 fm{sup -1}. Transition charge densities were extracted for natural-parity states from 0{sup +} up to 9{sup -} and up to an excitation energy of 3.5 MeV. For several new excited states spin and parity assignments have been suggested. The experimental transition charge densities have been interpreted with the aid of the quasiparticle-phonon model (QPM). The QPM is well-suited to investigate the contribution of collective and single-particle degrees of freedom to excited states in spherical nuclei. On the basis of the QPM calculations it is shown that in {sup 142}Nd both degrees of freedom play an important role, as well as the interplay between them. Both the strength distribution and the structure of the transition charge densities of the low-lying excited states are well described by the calculations. The origin of the structure in the nuclear interior usually predicted by microscopic calculations but not observed experimentally is explained. An argument for the proton number dependence of the excitation energy of the 3{sub 1}{sup -} state in the N=82 isotones is given. (orig.).
Characterization of the low-lying 0+ and 2+ states in Ni68 via β decay of the low-spin Co68 isomer
Flavigny, F; Radulov, D; Darby, I J; De Witte, H; Diriken, J; Fedorov, D V; Fedosseev, V N; Fraile, L M; Huyse, M; Ivanov, V S; Köster, U; Marsh, B A; Otsuka, T; Popescu, L; Raabe, R; Seliverstov, M D; Shimizu, N; Sjödin, A M; Tsunoda, Y; Van den Bergh, P; Van Duppen, P; Van de Walle, J; Venhart, M; Walters, W B; Wimmer, K
2015-01-01
The low-energy structure of the neutron-rich nucleus Ni68 has been investigated by measuring the β decay of the low-spin isomer in Co68 selectively produced in the decay chain of Mn68. A revised level scheme has been built based on the clear identification of β-γ-E0 delayed coincidences. Transitions between the three lowest-lying 0+ and 2+ states are discussed on the basis of measured intensities or their upper limits for unobserved branches and state-of-the-art shell model calculations.
Solvable quadratic Lie algebras
Institute of Scientific and Technical Information of China (English)
ZHU; Linsheng
2006-01-01
A Lie algebra endowed with a nondegenerate, symmetric, invariant bilinear form is called a quadratic Lie algebra. In this paper, the author investigates the structure of solvable quadratic Lie algebras, in particular, the solvable quadratic Lie algebras whose Cartan subalgebras consist of semi-simple elements, the author presents a procedure to construct a class of quadratic Lie algebras from the point of view of cohomology and shows that all solvable quadratic Lie algebras can be obtained in this way.
Astrophysical Constraints on Singlet Scalars at LHC
Hertzberg, Mark P
2016-01-01
We consider the viability of new heavy gauge singlet scalar particles at the LHC. Our motivation for this study comes from the possibility of a new particle with mass ~ 750 GeV decaying significantly into two photons at LHC, but our analysis applies more broadly. We show that there are significant constraints from astrophysics and cosmology on the simplest UV complete models that incorporate such a particle and its associated collider signal. The simplest and most obvious UV complete model that incorporates the signal is that it arises from a new singlet scalar (or pseudo-scalar) coupled to a new electrically charged and colored heavy fermion. Here we show that these new fermions (and anti-fermions) would be produced in the early universe, then form new color singlet heavy mesons with light quarks, obtain a non-negligible freeze-out abundance, and remain in kinetic equilibrium until decoupling. These heavy mesons possess interesting phenomenology, dependent on their charge, including forming new bound states ...
Comprehensive theoretical studies on the low-lying electronic states of NiF, NiCl, NiBr, and NiI.
Zou, Wenli; Liu, Wenjian
2006-04-21
The low-lying electronic states of the nickel monohalides, i.e., NiF, NiCl, NiBr, and NiI, are investigated by using multireference second-order perturbation theory with relativistic effects taken into account. For the energetically lowest 11 lambda-S states and 26 omega states there into, the potential energy curves and corresponding spectroscopic constants (vertical and adiabatic excitation energies, equilibrium bond lengths, vibrational frequencies, and rotational constants) are reported. The calculated results are grossly in very good agreement with those solid experimental data. In particular, the ground state of NiI is shown to be different from those of NiF, NiCl, and NiBr, being in line with the recent experimental observation. Detailed analyses are provided on those states that either have not been assigned or have been incorrectly assigned by previous experiments.
Institute of Scientific and Technical Information of China (English)
2008-01-01
The calculations on the potential energy curves and spectroscopic constants of the ground and low-lying excited states of BrCl+,one of the important molecular ions in environment science,have been performed by using the multireference configuration interaction method at high level of theory in quantum chemistry.Through analyses of the effects of the spin-orbit coupling interaction on the elec-tronic structures and spectroscopic properties,the multiconfiguration characteristic of the X2Π ground state and low-lying excited states was established.The spin-orbit coupling splitting energy of the X2 Π ground state was calculated to be 1814 cm-1,close to the experimental value 2070 cm-1.The spin-orbit coupling splitting energy of the 2Π(Ⅱ) exited state was predicted to be 766 cm-1.The transition dipole moments and Frank-Condon factors of the 3/2(Ⅲ)-X3/2 and 1/2(Ⅲ)-1/2(I) transitions were estimated,and the radiative lifetimes of the two transitions were briefly discussed.
Institute of Scientific and Technical Information of China (English)
WANG MingWei; WANG BingWu; CHEN ZhiDa
2008-01-01
The calculations on the potential energy curves and spectroscopic constants of the ground and low-lying excited states of BrCl+, one of the important molecular ions in environment science, have been performed by using the multireference configuration interaction method at high level of theory in quantum chemistry. Through analyses of the effects of the spin-orbit coupling interaction on the electronic structures and spectroscopic properties, the multiconfiguration characteristic of the X2∏ ground state and low-lying excited states was established. The spin-orbit coupling splitting energy of the X2∏ ground state was calculated to be 1814 cm-1, close to the experimental value 2070 cm-1. The spin-orbit coupling splitting energy of the 2∏(Ⅱ) exited state was predicted to be 766 cm-1. The transition dipole moments and Frank-Condon factors of the 3/2(Ⅲ)-X3/2 and 1/2(Ⅲ)-1/2(Ⅰ) transitions were estimated, and the radiative lifetimes of the two transitions were briefly discussed.
Bogdanchikov, Georgii A.; Baklanov, Alexey V.
2017-01-01
Ab initio calculations have been carried out to investigate interaction of titanium dioxide TiO2 with oxygen O2 in ground triplet and excited singlet states. On a singlet potential energy surface (PES) formation of a stable compound of titanium peroxide TiO4 is revealed which should appear in reaction of TiO2 with singlet oxygen without activation barrier. This peroxide is lower in energy than the ground state of two individual molecules TiO2 + 3O2 by 34.6 kcal/mol. Location of conical intersection between triplet and singlet PESs of TiO2sbnd O2 is also investigated.
Nuclear structure of low-lying states in 60,62,64,66Zn — A shell model description
Rai, S.; Biswas, A.; Mukherjee, B.
2016-11-01
Shell model calculation has been performed for even-even 60,62,64,66Zn using NuShellX code in f5/2pg9/2 model space with two different effective Hamiltonians, viz. JUN45 and jj44b. The low-lying structure is studied up to angular momentum, I = 10ℏ by calculating level energies, reduced transition probabilities, occupation numbers, lifetimes, and quadrupole moments. The results of the calculations are compared with the available experimental data. It is observed that the inclusion of 1g9/2 orbital in the model space is essential to understand nuclear structure in these isotopes. Shell model calculation with an improved set of effective Hamiltonian parameters and inclusion of 1f7/2 orbital in the model space are necessary in order to produce finer agreement with the experimental observations.
Lying despite telling the truth.
Wiegmann, Alex; Samland, Jana; Waldmann, Michael R
2016-05-01
According to the standard definition of lying an utterance counts as a lie if the agent believes the statement to be false. Thus, according to this view it is possible that a lie states something that happens to be true. This subjective view on lying has recently been challenged by Turri and Turri (2015) who presented empirical evidence suggesting that people only consider statements as lies that are objectively false (objective view). We argue that the presented evidence is in fact consistent with the standard subjective view if conversational pragmatics is taken into account. Three experiments are presented that directly test and support the subjective view. An additional experiment backs up our pragmatic hypothesis by using the uncontroversial case of making a promise.
β decay of Si,4038 (Tz=+5 ,+6 ) to low-lying core excited states in odd-odd P,4038 isotopes
Tripathi, Vandana; Lubna, R. S.; Abromeit, B.; Crawford, H. L.; Liddick, S. N.; Utsuno, Y.; Bender, P. C.; Crider, B. P.; Dungan, R.; Fallon, P.; Kravvaris, K.; Larson, N.; Macchiavelli, A. O.; Otsuka, T.; Prokop, C. J.; Richard, A. L.; Shimizu, N.; Tabor, S. L.; Volya, A.; Yoshida, S.
2017-02-01
Low-lying excited states in P,4038 have been identified in the β decay of Tz=+5 ,+6 , Si,4038. Based on the allowed nature of the Gamow-Teller (GT) decay observed, these states are assigned spin and parity of 1+ and are core-excited 1p1h intruder states with a parity opposite to the ground state. The occurrence of intruder states at low energies highlights the importance of pairing and quadrupole correlation energies in lowering the intruder states despite the N =20 shell gap. Configuration interaction shell model calculations with the state-of-art SDPF-MU effective interaction were performed to understand the structure of these 1p1h states in the even-A phosphorus isotopes. States in 40P with N =25 were found to have very complex configurations involving all the f p orbitals leading to deformed states as seen in neutron-rich nuclei with N ≈28 . The calculated GT matrix elements for the β decay highlight the dominance of the decay of the core neutrons rather than the valence neutrons.
Stochastic Lie group integrators
Malham, Simon J A
2007-01-01
We present Lie group integrators for nonlinear stochastic differential equations with non-commutative vector fields whose solution evolves on a smooth finite dimensional manifold. Given a Lie group action that generates transport along the manifold, we pull back the stochastic flow on the manifold to the Lie group via the action, and subsequently pull back the flow to the corresponding Lie algebra via the exponential map. We construct an approximation to the stochastic flow in the Lie algebra via closed operations and then push back to the Lie group and then to the manifold, thus ensuring our approximation lies in the manifold. We call such schemes stochastic Munthe-Kaas methods after their deterministic counterparts. We also present stochastic Lie group integration schemes based on Castell--Gaines methods. These involve using an underlying ordinary differential integrator to approximate the flow generated by a truncated stochastic exponential Lie series. They become stochastic Lie group integrator schemes if...
Universal doublet-singlet Higgs couplings and phenomenology at the CERN Large Hadron Collider
Bhattacharyya, Gautam; Nandi, S
2008-01-01
We consider a minimal extension of the Standard Model where a real, gauge singlet scalar field is added to the standard spectrum. Introducing the Ansatz of universality of scalar couplings, we are led to a scenario which has a set of very distinctive and testable predictions: (i) the mixing between the SM Higgs and the new state is near maximal, (ii) the ratio of the two Higgs mass eigenstates is fixed ($\\sim \\sqrt{3}$), (iii) the decay modes of each of the two eigenstates are Standard Model like. We also study how electroweak precision tests constrain this scenario. We predict the lighter Higgs to lie in the range of 114 and 145 GeV, and hence the heavier one between 198 and 250 GeV. The predictions of the model can be tested at the upcoming LHC.
Drenska, S B; Minkov, N
2002-01-01
We implement a high order discrete derivative analysis of the low lying collective energies of even-even nuclei with respect to the total number of valence nucleon pairs N in the framework of F- spin multiplets appearing in a symplectic sp(4,R) classification scheme. We find that for the nuclei of any given F- multiplet the respective experimental energies exhibit a Delta N=2 staggering behavior and for the nuclei of two united neighboring F- multiplets well pronounced Delta N=1 staggering patterns are observed. Those effects have been reproduced successfully through a generalized sp(4,R) model energy expression and explained in terms of the step-like changes in collective modes within the F- multiplets and the alternation of the F-spin projection in the united neighboring multiplets. On this basis we suggest that the observed Delta N=2 and Delta N=1 staggering effects carry detailed information about the respective systematic manifestation of both high order alpha - particle like quartetting of nucleons and ...
Theoretical investigation of the ground and low-lying excited states of nickel carbide, NiC.
Tzeli, Demeter; Mavridis, Aristides
2007-05-21
The electronic structure and bonding of 19 states of the diatomic nickel carbide (NiC) has been studied by multireference methods. Potential energy curves have been constructed for all states, whereas for the three lowest states of symmetries X (1)Sigma(+), a (3)Pi, and A (1)Pi well separated from the rest of the states, special attention was paid through the use of very large basis sets and the calculation of core-valence correlation and scalar relativistic effects. The recommended binding energies for these states are 91, 67, and 54 kcal/mol with respect to the ground state atoms. Our results in general can be considered in fair agreement with the limited experimental findings.
Institute of Scientific and Technical Information of China (English)
Gao Feng; Yang Chuan-Lu; Hu Zhen-Yan; Wang Mei-Shan
2007-01-01
The potential energy curves (PECs) of the ground state (3Π) and three low-lying excited states (1∑, 3∑,1Π) of CdSe dimer have been studied by emploging quasirelativistic effective core potentials on the basis of the complete active space self-consistent field method followed by multireference configuration interaction calculation. The four PECs are fitted to analytical potential energy functions using the Murrel-Sorbie potential function. Based on the PECs,the vibrational levels of the four states are determined by solving the Schr(o)dinger equation of nuclear motion, and corresponding spectroscopic contants are accurately calculated. The equilibrium positions as well as the spectroscopic constants and the vibrational levels are reported. By our analysis, the 3Π state, of which the dissociation asymptote is Cd(1S) + Se(3p), is identified as a ground state of CdSe dimer, and the corresponding dissociation energy is estimated to be 0.39eV. However, the first excited state is only 1132.49cm-1 above the ground state and the 3∑ state is the highest in the four calculated states.
New strategies to produce and detect singlet oxygen in a cell
DEFF Research Database (Denmark)
Gollmer, Anita
2012-01-01
Singlet oxygen, the first excited electronic state of molecular oxygen, plays a major role in oxygen-dependent photo-induced cell death. In such systems, singlet oxygen is generally produced in a photosensitized process wherein light is absorbed by a molecule (the so-called sensitizer) which...... of the general methodology to generate and detect singlet oxygen is currently of great importance in order to better understand the roles played by singlet oxygen in photo-induced cell death. From a mechanistic perspective, experiments performed at the level of a single cell provide unique insight...... of a new, commercially available fluorescent probe called Singlet Oxygen Sensor Green® (SOSG) was examined in this dissertation. The pertinent methodology involves a trapping reaction with singlet oxygen that in turn changes the fluorescence quantum yield of the probe. First, it is shown that the immediate...
Prodhan, Suryoday; Ramasesha, S
2016-01-01
Symmetry adapted density matrix renormalization group (SDMRG) technique has been an efficient method for studying low-lying eigenstates in one- and quasi-one dimensional electronic systems. However, SDMRG method had bottlenecks involving construction of linearly independent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. We have developed a modified algorithm to overcome this bottleneck. The new method incorporates end-to-end interchange symmetry ($C_2$), electron- hole symmetry (J) and parity symmetry (P ) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new basis with maximum sparseness, just one non-zero matrix element per row. Using methods similar to those employed in exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the eighties, it is possible to construct orthogonal SDMRG basis states while bypassi...
Yao, J M; Arteaga, D Pena; Ring, P; 10.1088/0256-307X/25/10/024
2008-01-01
A full three-dimensional angular momentum projection on top of a triaxial relativistic mean-Geld calculation is implemented for the first time. The underlying Lagrangian is a point coupling model and pairing correlations are taken into account by a monopole force. This method is applied for the low-lying excited states in 24Mg. Good agreement with the experimental data is found for the ground state properties. A minimum in the potential energy surface for the 2+ state, with beta = 0.55, gamma = 10 deg, is used as the basis to investigate the rotational energy spectrum as well as the corresponding B(E2) transition probabilities as compared to the available data.
The quantum coherent mechanism for singlet fission: experiment and theory.
Chan, Wai-Lun; Berkelbach, Timothy C; Provorse, Makenzie R; Monahan, Nicholas R; Tritsch, John R; Hybertsen, Mark S; Reichman, David R; Gao, Jiali; Zhu, X-Y
2013-06-18
The absorption of one photon by a semiconductor material usually creates one electron-hole pair. However, this general rule breaks down in a few organic semiconductors, such as pentacene and tetracene, where one photon absorption may result in two electron-hole pairs. This process, where a singlet exciton transforms to two triplet excitons, can have quantum yields as high as 200%. Singlet fission may be useful to solar cell technologies to increase the power conversion efficiency beyond the so-called Shockley-Queisser limit. Through time-resolved two-photon photoemission (TR-2PPE) spectroscopy in crystalline pentacene and tetracene, our lab has recently provided the first spectroscopic signatures in singlet fission of a critical intermediate known as the multiexciton state (also called a correlated triplet pair). More importantly, we found that population of the multiexciton state rises at the same time as the singlet state on the ultrafast time scale upon photoexcitation. This observation does not fit with the traditional view of singlet fission involving the incoherent conversion of a singlet to a triplet pair. However, it provides an experimental foundation for a quantum coherent mechanism in which the electronic coupling creates a quantum superposition of the singlet and the multiexciton state immediately after optical excitation. In this Account, we review key experimental findings from TR-2PPE experiments and present a theoretical analysis of the quantum coherent mechanism based on electronic structural and density matrix calculations for crystalline tetracene lattices. Using multistate density functional theory, we find that the direct electronic coupling between singlet and multiexciton states is too weak to explain the experimental observation. Instead, indirect coupling via charge transfer intermediate states is two orders of magnitude stronger, and dominates the dynamics for ultrafast multiexciton formation. Density matrix calculation for the crystalline
1,3-Diphenylisobenzofuran: a Model Chromophore for Singlet Fission
Energy Technology Data Exchange (ETDEWEB)
Johnson, Justin C [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Michl, Josef [University of Colorado; Academy of Sciences of the Czech Republic
2017-09-11
In this review we first provide an introductory description of the singlet fission phenomenon and then describe the ground and electronically excited states of the parent 1,3-diphenylisobenzofuran chromophore (1) and about a dozen of its derivatives. A discussion of singlet fission in thin polycrystalline layers of these materials follows. The highest quantum yield of triplet formation by singlet fission, 200% at 80 K, is found in one of the two known crystal modification of the parent. In the other modification and in many derivatives, excimer formation competes successfully and triplet yields are low. A description of solution photophysics of covalent dimers is described in the next section. Triplet yields are very low, but interesting phenomena are uncovered. One is an observation of a separated-charges (charge-transfer) intermediate in highly polar solvents. The other is an observation of excitation isomerism in both singlet and triplet states, where in one isomer the excitation is delocalized over both halves of the covalent dimer, whereas in the other it is localized on one of the halves. In the last section we present the operation of a simple device illustrating the use of triplets generated by singlet fission for charge separation.
Astrophysical constraints on singlet scalars at LHC
Hertzberg, Mark P.; Masoumi, Ali
2017-04-01
We consider the viability of new heavy gauge singlet scalar particles at colliders such as the LHC . Our original motivation for this study came from the possibility of a new heavy particle of mass ~ TeV decaying significantly into two photons at colliders, such as LHC, but our analysis applies more broadly. We show that there are significant constraints from astrophysics and cosmology on the simplest UV complete models that incorporate such new particles and its associated collider signal. The simplest and most obvious UV complete model that incorporates such signals is that it arises from a new singlet scalar (or pseudo-scalar) coupled to a new electrically charged and colored heavy fermion. Here we show that these new fermions (and anti-fermions) would be produced in the early universe, then form new color singlet heavy mesons with light quarks, obtain a non-negligible freeze-out abundance, and remain in kinetic equilibrium until decoupling. These heavy mesons possess interesting phenomenology, dependent on their charge, including forming new bound states with electrons and protons. We show that a significant number of these heavy states would survive for the age of the universe and an appreciable number would eventually be contained within the earth and solar system. We show that this leads to detectable consequences, including the production of highly energetic events from annihilations on earth, new spectral lines, and, spectacularly, the destabilization of stars. The lack of detection of these consequences rules out such simple UV completions, putting pressure on the viability of such new particles at LHC . To incorporate such a scalar would require either much more complicated UV completions or even further new physics that provides a decay channel for the associated fermion.
Application of electric field ionization method to detect the high-lying Rydberg states of Eu I
Institute of Scientific and Technical Information of China (English)
Jun Xie; Changjian Dai; Ming Li
2011-01-01
@@ The 4f76s(9S)np 8PJ (J = 5/2, 7/2, 9/2) Rydberg series converging to the first ionization limit 4f76s 9S4 of the Eu atom using the three-step laser excitation and electric-field-ionization (EFI) method are studied.First, the Eu atom is excited from the 4f76s2 8So7/2 ground state to the 4f76s7s 8So7/2 state through the 4f76s6p 10P9/2 state by the first two dye lasers.Next, it is populated to many higher-n members of the 4f76s(9S)np 8pJ Rydberg series by the third dye laser whose wavelength is scanned within a certain range.%The 4f76s(9S)np 8PJ (J = 5/2, 7/2, 9/2) Rydberg series converging to the first ionization limit 4f76s 9S4 of the Eu atom using the three-step laser excitation and electric-field-ionization (EFI) method are studied.First, the Eu atom is excited from the 4f76s2 8S7o/2 ground state to the 4f76s7s 8S7o/2 state through the 4f76s6p 10P9/2 state by the first two dye lasers. Next, it is populated to many higher-n members of the 4f76s(9S)np 8pJ Rydberg series by the third dye laser whose wavelength is scanned within a certain range.Finally, the atom in these higher-n states is ionized by the external pulsed electric field. With the field strength up to 2 kV/cm, we can detect the atom in 4f76s(9S)np 8pJ states with n ≥ 40. With the given laser line width, the level energies of Rydberg states with n as high as 72 can be determined. We not only confirm the previous data on the 4f76s(9S) np 8pJ Rydberg series, but also extend the n-value assignment significantly by detecting more states.
Christensen, Ronald L; Enriquez, Miriam M; Wagner, Nicole L; Peacock-Villada, Alexandra Y; Scriban, Corina; Schrock, Richard R; Polívka, Tomáš; Frank, Harry A; Birge, Robert R
2013-02-21
Steady-state and ultrafast transient absorption spectra were obtained for a series of conformationally constrained, isomerically pure polyenes with 5-23 conjugated double bonds (N). These data and fluorescence spectra of the shorter polyenes reveal the N dependence of the energies of six (1)B(u)(+) and two (1)A(g)(-) excited states. The (1)B(u)(+) states converge to a common infinite polyene limit of 15,900 ± 100 cm(-1). The two excited (1)A(g)(-) states, however, exhibit a large (~9000 cm(-1)) energy difference in the infinite polyene limit, in contrast to the common value previously predicted by theory. EOM-CCSD ab initio and MNDO-PSDCI semiempirical MO theories account for the experimental transition energies and intensities. The complex, multistep dynamics of the 1(1)B(u)(+) → 2(1)A(g)(-) → 1(1)A(g)(-) excited state decay pathways as a function of N are compared with kinetic data from several natural and synthetic carotenoids. Distinctive transient absorption signals in the visible region, previously identified with S* states in carotenoids, also are observed for the longer polyenes. Analysis of the lifetimes of the 2(1)A(g)(-) states, using the energy gap law for nonradiative decay, reveals remarkable similarities in the N dependence of the 2(1)A(g)(-) decay kinetics of the carotenoid and polyene systems. These findings are important for understanding the mechanisms by which carotenoids carry out their roles as light-harvesting molecules and photoprotective agents in biological systems.
Zhang, Qing-Qing; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang
2017-07-05
The potential energy curves and transition dipole moments for the 1(2)Σ(+), 2(2)Σ(+), 1(2)Π and 2(2)Π electronic states of the two molecules are calculated using multi-reference configuration interaction and the large basis sets aug-cc-pwCV5Z. Based on the obtained potential energy curves, the rotational and vibrational energy levels of the states are obtained by solving the Schrödinger equation of nuclear motion, and the spectroscopic parameters are then obtained by fitting the energy levels to Dunham series expansions. The spin-orbit coupling effect of the (2)Π states for both the BH(+) cation and BH(-) anion are calculated. Highly diagonally distributed Franck-Condon factors are determined for the 1(2)Σ(+) (v″=0)↔1(2)Π (v'=0) transition, ƒ00 (BH(+))=0.943, while the Franck-Condon factors for the 1(2)Π (v″=0)↔1(2)Σ(+) (v'=0) transition is ƒ00 (BH(-))=0.942. Moreover, the radiative lifetime of 38.2ns for the excited 1(2)Π state of the BH(+) and 91.8ns for the 1(2)Σ(+) state of the BH(-) are obtained, which are short enough for rapid laser cooling. A three-step optical scheme of the laser cooling is constructed for either the BH(+) cation or the BH(-) anion. Copyright © 2017 Elsevier B.V. All rights reserved.
The low-lying electronic states and optical schemes for the laser cooling of the BH+ and BH- ions
Zhang, Qing-Qing; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang
2017-07-01
The potential energy curves and transition dipole moments for the 12Σ+, 22Σ+, 12Π and 22Π electronic states of the two molecules are calculated using multi-reference configuration interaction and the large basis sets aug-cc-pwCV5Z. Based on the obtained potential energy curves, the rotational and vibrational energy levels of the states are obtained by solving the Schrödinger equation of nuclear motion, and the spectroscopic parameters are then obtained by fitting the energy levels to Dunham series expansions. The spin-orbit coupling effect of the 2Π states for both the BH+ cation and BH- anion are calculated. Highly diagonally distributed Franck-Condon factors are determined for the 12Σ+ (v″ = 0) ↔ 12Π (v‧ = 0) transition, ƒ00 (BH+) = 0.943, while the Franck-Condon factors for the 12Π (v″ = 0) ↔ 12Σ+ (v‧ = 0) transition is ƒ00 (BH-) = 0.942. Moreover, the radiative lifetime of 38.2 ns for the excited 12Π state of the BH+ and 91.8 ns for the 12Σ+ state of the BH- are obtained, which are short enough for rapid laser cooling. A three-step optical scheme of the laser cooling is constructed for either the BH+ cation or the BH- anion.
Advanced Singlet Oxygen Generator
2009-01-01
The laboratory of the participant is equipped with devices, facilities and methods for investigations of SOG. The personnel of participant...photodetectors) aproache to the steady state values (example of oscillogramms in Fig. 40-43). All results presented below obtained only for steady state...it into glass vessel containing 100 ml of distillated water. We tried to detect traces of KOH in this vessel by acid-base titration method . It was
Fragmentation of low-lying hexadecapole states in even /sup 74 -82/Se and a RPA calculation
Energy Technology Data Exchange (ETDEWEB)
Ogino, K.; Kadota, Y.; Haga, H. (Kyoto Univ. (Japan). Faculty of Engineering); Matsuki, S.; Higo, T.; Shiba, T. (Kyoto Univ. (Japan). Inst. for Chemical Research); Sakamoto, N. (Nara Women' s Univ. (Japan). Dept. of Physics); Okuma, Y. (Osaka Univ. (Japan). Research Center for Nuclear Physics); Yanabu, T. (Kanazawa Univ. (Japan). Faculty of Education)
1983-10-20
The level schemes of the even /sup 74 -82/Se up to Esub(X)=5.0 MeV have been investigated with high-resolution inelastic proton scattering at Esub(p)=64.8 MeV. Several 4/sup +/ states with comparable strengths were found at Esub(X)=2.0-5.0 MeV in all isotopes studied. The energy weighted sum-rule fraction of the 4/sup +/ states in this region increases with decreasing neutron number from /sup 82/Se (1.0%) up to /sup 76/Se (3.7%), and then decreases in /sup 74/Se (2.6%). A RPA calculation with a pairing plus hexadecapole-hexadecapole interaction can well reproduce the distribution of the excitation energies and transition strengths for the hexadecapole states.
Shayesteh, Alireza; Alavi, S. Fatemeh; Rahman, Moloud; Gharib-Nezhad, Ehsan
2017-01-01
Ab initio potential energy curves have been calculated for the X2Σ+, A2Π, B2Σ+, 12Δ, E2Π and D2Σ+ states of CaH using the multi-reference configuration interaction method with large active space and basis sets. Transition dipole moments were calculated at Ca-H distances from 2.0 a0 to 14.0 a0, and excited state lifetimes were obtained. Our theoretical transition dipole moments can be combined with the available experimental data on the X2Σ+, A2Π and B2Σ+ states to calculate Einstein A coefficients for all rovibronic transitions of CaH appearing in solar and stellar spectra.
Isospin Character of Low-Lying Pygmy Dipole States in Pb208 via Inelastic Scattering of O17 Ions
Crespi, F. C. L.; Bracco, A.; Nicolini, R.; Mengoni, D.; Pellegri, L.; Lanza, E. G.; Leoni, S.; Maj, A.; Kmiecik, M.; Avigo, R.; Benzoni, G.; Blasi, N.; Boiano, C.; Bottoni, S.; Brambilla, S.; Camera, F.; Ceruti, S.; Giaz, A.; Million, B.; Morales, A. I.; Vandone, V.; Wieland, O.; Bednarczyk, P.; Ciemała, M.; Grebosz, J.; Krzysiek, M.; Mazurek, K.; Zieblinski, M.; Bazzacco, D.; Bellato, M.; Birkenbach, B.; Bortolato, D.; Calore, E.; Cederwall, B.; Charles, L.; de Angelis, G.; Désesquelles, P.; Eberth, J.; Farnea, E.; Gadea, A.; Görgen, A.; Gottardo, A.; Isocrate, R.; Jolie, J.; Jungclaus, A.; Karkour, N.; Korten, W.; Menegazzo, R.; Michelagnoli, C.; Molini, P.; Napoli, D. R.; Pullia, A.; Recchia, F.; Reiter, P.; Rosso, D.; Sahin, E.; Salsac, M. D.; Siebeck, B.; Siem, S.; Simpson, J.; Söderström, P.-A.; Stezowski, O.; Theisen, Ch.; Ur, C.; Valiente-Dobón, J. J.
2014-07-01
The properties of pygmy dipole states in Pb208 were investigated using the Pb208(O17, O17'γ) reaction at 340 MeV and measuring the γ decay with high resolution with the AGATA demonstrator array. Cross sections and angular distributions of the emitted γ rays and of the scattered particles were measured. The results are compared with (γ, γ') and (p, p') data. The data analysis with the distorted wave Born approximation approach gives a good description of the elastic scattering and of the inelastic excitation of the 2+ and 3- states. For the dipole transitions a form factor obtained by folding a microscopically calculated transition density was used for the first time. This has allowed us to extract the isoscalar component of the 1- excited states from 4 to 8 MeV.
Isospin character of low-lying pygmy dipole states in 208Pb via inelastic scattering of 17O ions.
Crespi, F C L; Bracco, A; Nicolini, R; Mengoni, D; Pellegri, L; Lanza, E G; Leoni, S; Maj, A; Kmiecik, M; Avigo, R; Benzoni, G; Blasi, N; Boiano, C; Bottoni, S; Brambilla, S; Camera, F; Ceruti, S; Giaz, A; Million, B; Morales, A I; Vandone, V; Wieland, O; Bednarczyk, P; Ciemała, M; Grebosz, J; Krzysiek, M; Mazurek, K; Zieblinski, M; Bazzacco, D; Bellato, M; Birkenbach, B; Bortolato, D; Calore, E; Cederwall, B; Charles, L; de Angelis, G; Désesquelles, P; Eberth, J; Farnea, E; Gadea, A; Görgen, A; Gottardo, A; Isocrate, R; Jolie, J; Jungclaus, A; Karkour, N; Korten, W; Menegazzo, R; Michelagnoli, C; Molini, P; Napoli, D R; Pullia, A; Recchia, F; Reiter, P; Rosso, D; Sahin, E; Salsac, M D; Siebeck, B; Siem, S; Simpson, J; Söderström, P-A; Stezowski, O; Theisen, Ch; Ur, C; Valiente-Dobón, J J
2014-07-04
The properties of pygmy dipole states in 208Pb were investigated using the 208Pb(17O, 17O'γ) reaction at 340 MeV and measuring the γ decay with high resolution with the AGATA demonstrator array. Cross sections and angular distributions of the emitted γ rays and of the scattered particles were measured. The results are compared with (γ, γ') and (p, p') data. The data analysis with the distorted wave Born approximation approach gives a good description of the elastic scattering and of the inelastic excitation of the 2+ and 3- states. For the dipole transitions a form factor obtained by folding a microscopically calculated transition density was used for the first time. This has allowed us to extract the isoscalar component of the 1- excited states from 4 to 8 MeV.
An Ab Initio Study of the Low-Lying Doublet States of AgO and AgS
Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.
1990-01-01
Spectroscopic constants (D(sub o), r(sub e), mu(sub e), T(sub e)) are determined for the doublet states of AgO and AgS below approx. = 30000/cm. Large valence basis sets are employed in conjunction with relativistic effective core potentials (RECPs). Electron correlation is included using the modified coupled-pair functional (MCPF) and multireference configuration interaction (MRCI) methods. The A(sup 2)Sigma(sup +) - X(sup 2)Pi band system is found to occur in the near infrared (approx. = 9000/cm) and to be relatively weak with a radiative lifetime of 900 microns for A(sup 2)Sigma(sup +) (upsilon = 0). The weakly bound C(sup 2)Pi state (our notation), the upper state of the blue system, is found to require high levels of theoretical treatment to determine a quantitatively accurate potential. The red system is assigned as a transition from the C(sup 2)Pi state to the previously unobserved A(sup 2)Sigma(sup +) state. Several additional transitions are identified that should be detectable experimentally. A more limited study is performed for the vertical excitation spectrum of AgS. In addition, a detailed all-electron study of the X(sup 2)Pi and A(sup 2)Sigma(sup +) states of AgO is carried out using large atomic natural orbital (ANO) basis sets. Our best calculated D(sub o) value for AgO is significantly less than the experimental value, which suggests that there may be some systematic error in the experimental determination.
Matrix elements in the coupled-cluster approach - With application to low-lying states in Li
Martensson-Pendrill, Ann-Marie; Ynnerman, Anders
1990-01-01
A procedure is suggested for evaluating matrix elements of an operator between wavefunctions in the coupled-cluster form. The use of the exponential ansatz leads to compact exponential expressions also for matrix elements. Algorithms are developed for summing all effects of one-particle clusters and certain chains of two-particle clusters (containing the well-known random-phase approximation as a subset). The treatment of one-particle perturbations in single valence states is investigated in detail. As examples the oscillator strength for the 2s-2p transition in Li as well as the hyperfine structure for the two states are studied and compared to earlier work.
Institute of Scientific and Technical Information of China (English)
Zhang Meng; Gou Bing-Cong
2005-01-01
Variational calculations are carried out with a multiconfiguration-interaction wavefunction on the 1s22p2p 1De and 1s22p3p 3pe states to obtain the energies including the mass polarization and relativistic corrections for the beryllium isoelectronic sequence (Z=4-10). The oscillator strengths, transition rates and wavelengths are also calculated. Our results are compared with other theoretical and experimental data in the literatures. The fine structure and hyperfine structure of 1s22p3p 3pe state are also explored.
Gravitating fluids with Lie symmetries
Msomi, A M; Maharaj, S D
2010-01-01
We analyse the underlying nonlinear partial differential equation which arises in the study of gravitating flat fluid plates of embedding class one. Our interest in this equation lies in discussing new solutions that can be found by means of Lie point symmetries. The method utilised reduces the partial differential equation to an ordinary differential equation according to the Lie symmetry admitted. We show that a class of solutions found previously can be characterised by a particular Lie generator. Several new families of solutions are found explicitly. In particular we find the relevant ordinary differential equation for all one-dimensional optimal subgroups; in several cases the ordinary differential equation can be solved in general. We are in a position to characterise particular solutions with a linear barotropic equation of state.
Lies and Deception: A Failed Reconciliation
DEFF Research Database (Denmark)
Broncano-Berrocal, Fernando
2013-01-01
The traditional view of lying says that lying is a matter of intending to deceive others by making statements that one believes to be false. Jennifer Lackey has recently defended the following version of the traditional view: A lies to B just in case (i) A states that p to B, (ii) A believes that...... is false and (iii) A intends to be deceptive to B in stating that p. I argue that, despite all the virtues that Lackey ascribes to her view, conditions (i), (ii) and (iii) are not sufficient for lying.......The traditional view of lying says that lying is a matter of intending to deceive others by making statements that one believes to be false. Jennifer Lackey has recently defended the following version of the traditional view: A lies to B just in case (i) A states that p to B, (ii) A believes that p...
A CCBA description of the (p, t) reaction to low-lying O+ states in the Ge isotopes
Becker, A.; Alderliesten, C.; Bakkum, E.A.; Borg, K. van der; Engelen, C.P.M. van; Zybert, L.; Kamermans, R.
1982-01-01
Differential cross sections for the (p, t) reaction to 0+ states in the even Ge isotopes have been measured at an incident energy (Ep = 13 MeV) where the triton energy is below the Coulomb barrier. The data are described by a coupled-channels calculation with wave functions consisting of neutron
Zhang, Qing-Qing; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang
2017-10-01
The potential energy curves and transition dipole moments of 12Σ+, 22Σ+, 12Π and 22Π states of NH+ cation and NH- anion are calculated by using multi-reference configuration interaction method and large all-electron basis sets. Based on the obtained potential energy curves, the rotational and vibrational energy levels of the states are obtained by solving the Schrödinger equation of nuclear movement. The calculated spectroscopic parameters for NH+ cation and NH- anion are in good agreement with available theoretical and experimental results. The spin orbit coupling effect of the 2Π states for both NH+ cation and NH- anion are calculated. The feasibility of laser cooling of the two molecules is examined by using the results of the molecular structure and spectroscopy. The highly diagonal Franck-Condon factors for the 12Π (v″ = 0) ↔ 12Σ+ (v‧ = 0) transition of NH+ and NH- are 0.821 and 0.999, while the radiative lifetimes of the 12Σ+ (v‧ = 0) state for the two molecules are 384 ns and 52.4 ns, respectively. The results indicate that NH+ cation and NH- anion are good candidate molecules for laser cooling. The cooling scheme via Sisyphus process for the NH+ cation and NH- anion are proposed in the paper. The laser wavelengths for the close cycles of the absorption and radiation are also determined. Unfortunately, the potential energy curve of the ground state of the neutral NH molecule shows that the auto-detachment of NH- anion is possible, implying the optical scheme of laser cooling for NH- anion is not easy to achieve in the experiment although it has larger Franck-Condon factor.
Zhang, Qing-Qing; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang
2017-10-05
The potential energy curves and transition dipole moments of 1(2)Σ(+), 2(2)Σ(+), 1(2)Π and 2(2)Π states of NH(+) cation and NH(-) anion are calculated by using multi-reference configuration interaction method and large all-electron basis sets. Based on the obtained potential energy curves, the rotational and vibrational energy levels of the states are obtained by solving the Schrödinger equation of nuclear movement. The calculated spectroscopic parameters for NH(+) cation and NH(-) anion are in good agreement with available theoretical and experimental results. The spin orbit coupling effect of the (2)Π states for both NH(+) cation and NH(-) anion are calculated. The feasibility of laser cooling of the two molecules is examined by using the results of the molecular structure and spectroscopy. The highly diagonal Franck-Condon factors for the 1(2)Π (v″=0)↔1(2)Σ(+) (v'=0) transition of NH(+) and NH(-) are 0.821 and 0.999, while the radiative lifetimes of the 1(2)Σ(+) (v'=0) state for the two molecules are 384ns and 52.4ns, respectively. The results indicate that NH(+) cation and NH(-) anion are good candidate molecules for laser cooling. The cooling scheme via Sisyphus process for the NH(+) cation and NH(-) anion are proposed in the paper. The laser wavelengths for the close cycles of the absorption and radiation are also determined. Unfortunately, the potential energy curve of the ground state of the neutral NH molecule shows that the auto-detachment of NH(-) anion is possible, implying the optical scheme of laser cooling for NH(-) anion is not easy to achieve in the experiment although it has larger Franck-Condon factor. Copyright © 2017 Elsevier B.V. All rights reserved.
Koh, Yang Wei
2016-04-01
We present an extensive numerical study of the Sherrington-Kirkpatrick model in a transverse field. Recent numerical studies of quantum spin glasses have focused on exact diagonalization of the full Hamiltonian for small systems (≈20 spins). However, such exact numerical treatments are difficult to apply on larger systems. We propose making an approximation by using only a subspace of the full Hilbert space spanned by low-lying excitations consisting of one-spin-flipped and two-spin-flipped states. The approximation procedure is carried out within the theoretical framework of the Hartree-Fock approximation and configuration interaction. Although not exact, our approach allows us to study larger system sizes comparable to that achievable by state-of-the-art quantum Monte Carlo simulations. We calculate two quantities of interest due to recent advances in quantum annealing, the ground-state energy and the energy gap between the ground and first excited states. For the energy gap, we derive a formula that enables it to be calculated using just the ground-state wave function, thereby circumventing the need to diagonalize the Hamiltonian. We calculate the scalings of the energy gap and the leading correction to the extensive part of the ground-state energy with system size, which are difficult to obtain with current methods.
Monmonier, Mark
2005-01-01
Darrell Huff’s How to Lie with Statistics was the inspiration for How to Lie with Maps, in which the author showed that geometric distortion and graphic generalization of data are unavoidable elements of cartographic representation. New examples of how ill-conceived or deliberately contrived statistical maps can greatly distort geographic reality demonstrate that lying with maps is a special case of lying with statistics. Issues addressed include the effects of map scale on geometry and featu...
Properties of low-lying intruder states in 34Aland 34Sipopulated in the beta-decay of 34Mg
Lică, R; Negoită, F; Grévy, S; Mărginean, N; Desagne, Ph; Stora, T; Borcea, C; Borcea, R; Călinescu, S; Daugas, J M; Filipescu, D; Kuti, I; Fraile, L M; Franchoo, S; Gheorghe, I; Ghită, D G; Mărginean, R; Mihai, C; Mourface, P; Morel, P; Mrazek, J; Negret, A; Pietreanu, D; Sava, T; Sohler, D; Stănoiu, M; Stefan, I; Şuvăilă, R; Toma, S; Ur, C A
2015-01-01
The results of the IS530 experiment at ISOLDE revealed new information concerning several nuclei close to the N ≈ 20 'Island of Inversion' - 34Mg, 34Al, 34Si. The half-life of 34Mgwas found to be three times larger than the adopted value (63(1) ms instead of 20(10) ms). The beta-gamma spectroscopy of 34Mgperformed for the first time in this experiment, led to the first experimental level scheme for 34Al, also showing that the full beta strength goes through the predicted 1+ isomer in 34Al[1] and/or excited states that deexcite to it. The subsequent beta-decay of the 1+ isomer in 34Alallowed the observation of new gamma lines in 34Si, (tentatively) associated with low-spin high-energy excited states previously unobserved.
Experimental Study of Two-Alpha Emission from High-Lying Excited States of 17＇18^Ne
Institute of Scientific and Technical Information of China (English)
徐新星; 林承键; 贾会明; 杨峰; 贾飞; 吴振东; 张世涛; 刘祖华; 张焕乔; 徐瑚珊; 孙志宇; 王建松; 胡正国; 王猛; 陈若富; 张雪荧; 李琛; 雷祥国; 徐治国; 肖国青
2012-01-01
The experiments of two-alpha emission from 17,18^Ne excited levels were performed at the HIRFL-RIBLL facility of the Institute of Modern Physics, Lanzhou. The beams of 17^Ne at the energy of 49.9 MeV/u and lSNe at 51.8 MeV/u bombarded a 197Au target to populate excited states of 17,18^Ne via Coulomb excitation. Complete kinematics measurements were achieved by the detectors of a silicon strip and CsI＋PIN array. The experimental results combined with simple MC simulations show the characteristic of sequential two-alpha emission via 140 excited states for lSNe. The results of two-alpha emission from 17^Ne are preliminary and need further analyses.
Rates and singlet/triplet ratios from TADF transients
Nelson, Mitchell C
2016-01-01
Thermally activated delayed fluorescence has been reported in a number of OLED emitter materials engineered to have low singlet-triplet energy gaps. Here we derive closed solutions for steady state and transient behaviors and apply these results to data provided in recent reports. Earlier work has used yields, rates and a supplied forward crossing rate to estimate the reverse crossing rate and then obtain the singlet-triplet energy gap in a log-linear fit. In this work we use only the system relaxation times and obtain all five of the system constants: the singlet and triplet relaxation rates, the forward and reverse crossing rates and the singlet-triplet energy gap. These are then used to calculate the fluorescent/phosphorescent ratio and the singlet/triplet population ratio. Good fits are obtained for data from 4CzIPN and from the excimer m-MTDATA:t-Bu-PBD and the results appear to be consistent with the reported behaviors of OLEDS using these materials.
Collective aspects of singlet fission in molecular crystals
Energy Technology Data Exchange (ETDEWEB)
Teichen, Paul E.; Eaves, Joel D., E-mail: joel.eaves@colorado.edu [Department of Chemistry and Biochemistry, The University of Colorado at Boulder, Boulder, Colorado 80309 (United States)
2015-07-28
We present a model to describe collective features of singlet fission in molecular crystals and analyze it using many-body theory. The model we develop allows excitonic states to delocalize over several chromophores which is consistent with the character of the excited states in many molecular crystals, such as the acenes, where singlet fission occurs. As singlet states become more delocalized and triplet states more localized, the rate of singlet fission increases. We also determine the conditions under which the two triplets resulting from fission are correlated. Using the Bethe Ansatz and an entanglement measure for indistinguishable bipartite systems, we calculate the triplet-triplet entanglement as a function of the biexciton interaction strength. The biexciton interaction can produce bound biexciton states and provides a source of entanglement between the two triplets even when the triplets are spatially well separated. Significant entanglement between the triplet pair occurs well below the threshold for bound pair formation. Our results paint a dynamical picture that helps to explain why fission has been observed to be more efficient in molecular crystals than in their covalent dimer analogues and have consequences for photovoltaic efficiency models that assume that the two triplets can be extracted independently.
Goudreau, E. S.; Tokaryk, Dennis W.; Ross, Stephen Cary; Billinghurst, Brant E.
2016-06-01
Despite being an important prototype molecule for intramolecular proton tunnelling, the far-IR spectrum of the internally hydrogen-bonded species malonaldehyde (C_3O_2H_4) is not yet well understood. In the talk I gave at the ISMS meeting in 2015 I discussed the high-resolution spectra we obtained at the Canadian Light Source synchrotron in Saskatoon, Saskatchewan. These spectra include a number of fundamental vibrational bands in the 100-2000 cm-1 region. In our efforts to analyze these bands we have noticed that our ground state combination differences show a large drift (up to an order of magnitude larger than our experimental error) away from those calculated using constants established by Baba et al., particularly in regions of high J (above 30) and low Ka (below 5). An examination of the previous microwave and far-IR studies reveals that this region of J-Ka space was not represented in the lines that Baba et al. used to generate the values for their fitting parameters. By including our own measurements in the fitting, we were able to improve the characterization of the ground state so that it is now consistent with all of the existing data. This characterization now covers a much larger range of J-Ka space and has enabled us to make significant progress in analyzing our far-IR synchrotron spectra. These include an excited vibrational state at 241 cm-1 as well as several states split by the tunnelling effect at higher wavenumber. T. Baba, T. Tanaka, I. Morino, K. M. T. Yamada, K. Tanaka. Detection of the tunneling-rotation transitions of malonaldehyde in the submillimeter-wave region. J. Chem. Phys., 110. 4131-4133 (1999) P. Turner, S. L. Baughcum, S. L. Coy, Z. Smith. Microwave Spectroscopic Study of Malonaldehyde. 4. Vibration-Rotation Interaction in Parent Species. J. Am. Chem. Soc., 106. 2265-2267 (1984) D. W. Firth, K. Beyer, M. A. Dvorak, S. W. Reeve, A. Grushow, K. R. Leopold. Tunable far-infrared spectroscopy of malonaldehyde. J. Chem. Phys., 94. 1812
Isotope effects of ground and lowest lying vibrational states of H 3 - x D x O2 - complexes
Ansari, Narjes; Meyer, Hans-Dieter
2016-02-01
Isotope effects of the H 3 O2 - anion are investigated. For this, the 24 lowest excited vibrational states of the H 3 - x D x O2 - complexes, with x = 0-3, are computed using two different Hamiltonians, namely, a 7D reduced-dimensionality one with a numerical representation of the kinetic energy operator (KEO) and a 9D full-dimensionality Hamiltonian with an exact analytic KEO. The computations are carried out with the multiconfiguration time-dependent Hartree method. The obtained results show that bridge and terminal H-D exchange cause a variation in energy with or without a rearrangement of states. A clear rearrangement of fundamental modes is observed in bridge H-D exchange of the H 3 O2 - complex, where the frequency of bridge hydrogen stretching (z) is strongly lowered by substitution. The isotope effects show that rotation (ϕ), rocking (u1 + u2), wagging (u1 - u2), and O-O stretch (R) modes are sensitive to terminal H-D exchange, while the bridge-atom bending (x,y) and stretch (z) modes are sensitive to bridge H-D exchange. An influence coefficient, which measures the influence of an excitation of one mode on the various 1D reduced densities, is defined and analyzed in detail. It is shown that the D 3 O2 - complex is more strongly correlated or coupled than the other isotopologues.
Zhang, Lin; Zhang, Weiping
2016-10-01
A variety of dynamics in nature and society can be approximately treated as a driven and damped parametric oscillator. An intensive investigation of this time-dependent model from an algebraic point of view provides a consistent method to resolve the classical dynamics and the quantum evolution in order to understand the time-dependent phenomena that occur not only in the macroscopic classical scale for the synchronized behaviors but also in the microscopic quantum scale for a coherent state evolution. By using a Floquet U-transformation on a general time-dependent quadratic Hamiltonian, we exactly solve the dynamic behaviors of a driven and damped parametric oscillator to obtain the optimal solutions by means of invariant parameters of Ks to combine with Lewis-Riesenfeld invariant method. This approach can discriminate the external dynamics from the internal evolution of a wave packet by producing independent parametric equations that dramatically facilitate the parametric control on the quantum state evolution in a dissipative system. In order to show the advantages of this method, several time-dependent models proposed in the quantum control field are analyzed in detail.
The Higgs singlet extension at LHC Run 2
Chalons, Guillaume; Robens, Tania; Stefaniak, Tim
2016-01-01
We discuss the current status of theoretical and experimental constraints on the real Higgs singlet extension of the Standard Model. For the second neutral (non-standard) Higgs boson the full mass range from 1 GeV to 1 TeV accessible at past and current collider experiments is considered. We present benchmark scenarios for searches for an additional Higgs state in the real Higgs singlet extension of the Standard Model in Run 2 of the LHC. We furthermore discuss electroweak corrections to the H to hh partial decay width within this model.
Impurities near an antiferromagnetic-singlet quantum critical point
Mendes-Santos, T.; Costa, N. C.; Batrouni, G.; Curro, N.; dos Santos, R. R.; Paiva, T.; Scalettar, R. T.
2017-02-01
Heavy-fermion systems and other strongly correlated electron materials often exhibit a competition between antiferromagnetic (AF) and singlet ground states. Using exact quantum Monte Carlo simulations, we examine the effect of impurities in the vicinity of such an AF-singlet quantum critical point (QCP), through an appropriately defined "impurity susceptibility" χimp. Our key finding is a connection within a single calculational framework between AF domains induced on the singlet side of the transition and the behavior of the nuclear magnetic resonance (NMR) relaxation rate 1 /T1 . We show that local NMR measurements provide a diagnostic for the location of the QCP, which agrees remarkably well with the vanishing of the AF order parameter and large values of χimp.
Lee, Edmond P F; Dyke, John M; Mok, Daniel K W; Chau, Foo-tim
2008-05-15
A variety of density functional theory and ab initio methods, including B3LYP, B98, BP86, CASSCF, CASSCF/RS2, CASSCF/MRCI, BD, BD(T), and CCSD(T), with ECP basis sets of up to the quintuple-zeta quality for Y, have been employed to study the X(2)B2 state of YO2 and the X(1)A1 state of YO2(-). Providing that the Y 4s(2)4p(6) outer-core electrons are included in the correlation treatment, the RCCSD(T) method gives the most consistent results and is concluded to be the most reliable and practical computational method for YO2 and YO2(-). In addition, RCCSD(T) potential energy functions (PEFs) of the X(2)B2 state of YO2 and the X(1)A1 state of YO2(-) were computed, employing the ECP28MDF_aug-cc-pwCVTZ and aug-cc-pVTZ basis sets for Y and O, respectively. Franck-Condon factors, which include allowance for Duschinsky rotation and anharmonicity, were calculated using the computed RCCSD(T) PEFs and were used to simulate the first photodetachment band of YO2(-). The simulated spectrum matches very well with the corresponding experimental 355 nm photodetachment spectrum of Wu, H.; Wang, L.-S. J. Phys. Chem. A 1998, 102, 9129, confirming the reliability of the RCCSD(T) PEFs used. Further calculations on low-lying electronic states of YO2 gave T(e)'s and T(vert)'s of the A(2)A1, B(2)B1, and C(2)A2 states of YO2, as well as EAs and VDEs to these states from the X(1)A1 state of YO2(-). On the basis of the ab initio VDEs obtained in the present study, previous assignments of the second and third photodetachment bands of YO2(-) have been revised.
[Photosensitized luminescence of singlet oxygen in aqueous solutions].
Krasnovskiĭ, A A
1979-01-01
The photoluminescence of singlet oxygen has been observed in air saturated solutions of riboflavin in D2O and mixtures of D2O and H2O. The excitation spectrum coincides with the absorption spectrum of the pigment, the emission maximum lies at 1275 nm. In D2O the quantum yield is approximately 1,2 x 10(-7). H2O quenches the luminescence. Analysis of quenching has shown that the quantum yield in H2O is less than in D2O by the factor of 20.
Explorative computational study of the singlet fission process
Havenith, Remco W. A.; de Gier, Hilde D.; Broer, Ria
2012-01-01
Different ab initio methods, namely multi-reference and nonorthogonal configuration interaction techniques, are explored for their applicability in studying the singlet fission problem. It has been shown for 2-methyl-1,5-hexadiene that the (TT)-T-1 state can be identified using multi-reference techn
Universal higher order singlet QED corrections to unpolarized lepton scattering
Energy Technology Data Exchange (ETDEWEB)
Bluemlein, J. [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany); Kawamura, H. [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany)]|[Radiation Laboratory, RIKEN (Japan)
2006-12-15
We calculate the universal flavor-singlet radiative QED corrections to unpolarized lepton scattering applicable to general differential scattering cross sections, involving charged fermions or photons in initial or final states. The radiators are derived to O(({alpha} ln (Q{sup 2}/m{sub f}{sup 2})){sup 5}) in analytic form. Numerical illustrations are given. (orig.)
Energy Technology Data Exchange (ETDEWEB)
Barik, N.; Dash, B.K.
1986-04-01
Under the assumption that baryons are an assembly of independent quarks, confined in a first approximation by an effective potential U(r) = 1/2(1+..gamma../sup 0/)(ar/sup 2/+V/sub 0/ ) which presumably represents the nonperturbative gluon interactions, the mass spectrum of the low-lying ground-state baryons has been calculated by considering perturbatively the contributions of the residual quark-pion coupling arising out of the requirement of chiral symmetry and that of the quark-gluon coupling due to one-gluon exchange over and above the necessary center-of-mass correction. The physical masses of the baryons so obtained agree quite well with the corresponding experimental value. The strong coupling constant ..cap alpha../sub c/ = 0.58 required here to describe the QCD mass splittings is quite consistent with the idea of treating one-gluon-exchange effects in lowest-order perturbation theory.
Pugh, J. V.; Shen, K. K.; Winstead, C. B.; Gole, J. L.
1996-01-01
The first laser based probe for the sodium and lithium monoxides is established. The Li(Na)+N 2O reactions studied in a multiple collision entrainment mode produce the LiO and NaO ground X 2Π and low-lying monoxide excited states. In contrast to the alkali halides, laser induced excitation spectroscopy confirms that the LiO and NaO B 2Π states, counter to recent predictions, are located at energies well below the ground state dissociation asymptote and, as predicted, possess significant binding energies. An assignment of the laser induced excitation spectra (LIF) for the B 2Π-X 2Π transitions of LiO in the region 3940-4300 Å is based on a direct correlation with the observed chemiluminescence (CL) from the lowest level of the LiO B 2Π state ( ˜4000-7000 Å) and high quality ab initio calculations for the ground state. The self-consistent assignment of the observed LIF and CL spectra makes use of the complimentary extended progressions in the X 2Π (CL) and B 2Π (LIF) vibrational level structure which results from the significant shift of the B 2Π excited state potential relative to that of the ground state. The experimental data are consistent with an excited state vibrational frequency separation of order 130 cm -1, and T e( B2Π) ≈ 26078 ± 800 cm-1. The latter value, in correlation with the ground state dissociation energy of LiO, suggests a B 2Π excited state dissociation energy well in excess of 2000 cm -1. The radiative lifetimes of the lowest levels of the LiO B 2Π state, isoergic with the highest levels of the LiO ground state, are determined to be in excess of 600 ns. The corresponding NaO excitation spectra in the range 6680-7250 Å also correlate well with ab initio calculations for the ground electronic state of NaO. Within this study, we provide optical signatures which one might consider to monitor LiO or NaO in process streams. In correlation with the observed chemiluminescence from B 2Π states of the higher alkali oxides KO, RbO, and
Small -x behavior of the non-singlet and singlet structure functions g_1
Ermolaev, B I; Troyan, S I
2003-01-01
Explicit expressions for the non-singlet and singlet structure functions g_1 at the small $x$-region are obtained. They include the total resummation of double-logarithmic contributions and accounting for the running QCD coupling effects. We predict that both the non-singlet and singlet g_1 asymptotically ~ x^{- \\Delta}, with the singlet intercept = 0.86 and being more than twice larger than the non-singlet intercept = 0.4. The impact of the initial quark and gluon densities on the sign of g_1 at x << 1 is discussed.
A low-lying long-lived (26±1 ms) isomer in $^{34}$Al has been observed recently and assigned as 1$^{+}$ state of intruder character. It was populated in $^{36}$S fragmentation and feeds, in $\\beta$-decay, the 0$_{2}^{+}$ state in $^{34}$Si whose excitation energy and lifetime were determined in an electron-positron pairs spectroscopy experiment. In the present experiment we intend to measure for the first time the $\\gamma$-rays following the $\\beta$-decay of $^{34}$Mg. Despite the interest for $^{34}$Mg, the up-right corner of the “N$\\thicksim$20 island of inversion”, the only information on its $\\beta$-decay is the lifetime of 20±10 ms, determined from $\\beta$-neutron coincidences. As a result of the proposed experiment, we expect to place the first transitions in the level scheme of $^{34}$Al and to strongly populate the newly observed isomer, measuring its excitation energy, if the branching ratio to 4$^{−}$ ground state is significant. Theoretical estimations for the $\\beta$-decay of the new isome...
Xing, Wei; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue
2017-10-01
This paper studied the spectroscopic and transition properties of 36 low-lying states, which came from the first two dissociation limits of B2 molecule. The potential energy curves were calculated with the complete active space self-consistent field (CASSCF) method, which was followed by the internally contracted multireference configuration interaction (icMRCI) plus Davidson modification (icMRCI + Q) approach. Of these 36 states, the 25Σu-, 15Σu+, 25Πu, and 15Δu states were repulsive; the B3Δu, E3Σu+, f1Σu-, g1Πg, 23Πu, 33Σg-, 33Πu, 15Πg, and 33Σu+ states had double wells; the B3Δu, E3Σu+, G3Σu+, f1Σu-, g1Πg, 33Σg-, 23Πu, 33Πu, 15Πg, 25Πg, 25Σg-, and 33Σu+ states had one barrier; the 25Σg- state and the second wells of B3Δu, E3Σu+, 15Πg, f1Σu-, g1Πg, and 23Πu states were weakly bound; and the 25Σg- state had no vibrational levels. The avoided crossings existed between the B3Δu and 23Δu states, the E3Σu+ and G3Σu+ states, the G3Σu+ and 33Σu+ states, the 33Σu+ and 43Σu+ states, the 23Πu and 33Πu states, the g1Πg and 21Πg states, the 23Σg- and 33Σg- states, the 15Πg and 25Πg states, the 25Πg and 35Πg states, the 25Σg- and 35Σg- states, as well as the F3Πg and 33Πg states. Core-valence correlation and scalar relativistic corrections were taken into account. The extrapolation to the complete basis set limit was done. The spectroscopic parameters and vibrational properties were obtained. The transition dipole moments were calculated. Franck-Condon factors of some transitions were evaluated. The spin-orbit coupling (SOC) effect on the spectroscopic parameters and vibrational properties is tiny and sometimes even can be negligible. The results determined in this paper can provide some powerful guidelines to observe these states, in particular the states which have not been studied in the experiment.
Additive Lie ($\\xi$-Lie) Derivations and Generalized Lie ($\\xi$-Lie) Derivations on Prime Algebras
Qi, Xiaofei
2010-01-01
The additive (generalized) $\\xi$-Lie derivations on prime algebras are characterized. It is shown, under some suitable assumption, that an additive map $L$ is an additive (generalized) Lie derivation if and only if it is the sum of an additive (generalized) derivation and an additive map from the algebra into its center vanishing all commutators; is an additive (generalized) $\\xi$-Lie derivation with $\\xi\
Pravdivtsev, Andrey N; Yurkovskaya, Alexandra V; Vieth, Hans-Martin; Ivanov, Konstantin L
2016-01-01
We propose a robust and highly efficient NMR technique to create singlet spin order from longitudinal spin magnetization in coupled spin-1/2 pairs and to perform backward conversion (singlet order)$\\to$magnetization. In this method we exploit adiabatic switching of an RF-field in order to drive transitions between the singlet state and the $T_\\pm$ triplet states of a spin pair under study. We demonstrate that the method works perfectly for both strongly and weakly coupled spin pairs, providing a conversion efficiency between the singlet spin order and magnetization, which is equal to the theoretical maximum. We anticipate that the proposed technique is useful for generating long-lived singlet order, for preserving spin hyperpolarization and for assessing singlet spin order in nearly equivalent spin pairs in specially designed molecules and in low-field NMR studies.
Samanta, Pralok Kumar
2017-02-28
The rates for up-conversion intersystem crossing (UISC) from the T1 state to the S1 state are calculated for a series of organic emitters with an emphasis on thermally activated delayed fluorescence (TADF) materials. Both the spin-orbit coupling and the energy difference between the S1 and T1 states (ΔEST) are evaluated, at the density functional theory (DFT) and time-dependent DFT levels. The calculated UISC rates and ΔEST values are found to be in good agreement with available experimental data. Our results underline that small ΔEST values and sizable spin-orbit coupling matrix elements have to be simultaneously realized in order to facilitate UISC and ultimately TADF. Importantly, the spatial separation of the highest occupied and lowest unoccupied molecular orbitals of the emitter, a widely accepted strategy for the design of TADF molecules, does not necessarily lead to a sufficient reduction in ΔEST; in fact, either a significant charge-transfer (CT) contribution to the T1 state or a minimal energy difference between the local-excitation and charge-transfer triplet states is required to achieve a small ΔEST. Also, having S1 and T1 states of a different nature is found to strongly enhance spin-orbit coupling, which is consistent with the El-Sayed rule for ISC rates. Overall, our results indicate that having either similar energies for the local-excitation and charge-transfer triplet states or the right balance between a substantial CT contribution to T1 and somewhat different natures of the S1 and T1 states, paves the way toward UISC enhancement and thus TADF efficiency improvement.
Energy Technology Data Exchange (ETDEWEB)
Pore, J.L.; Cross, D.S.; Andreoiu, C.; Ashley, R.; Chester, A.S.; Noakes, B.; Starosta, K.; Voss, P.J. [Simon Fraser University, Department of Chemistry, Burnaby BC (Canada); Ball, G.C.; Bender, P.C.; Garnsworthy, A.B.; Hackman, G.; Rajabali, M.M. [TRIUMF, Vancouver BC (Canada); Diaz Varela, A.; Demand, G.A.; Dunlop, R.; Garrett, P.E.; Hadinia, B.; Jigmeddorj, B.; Laffoley, A.T.; Liblong, A.; Svensson, C.E. [University of Guelph, Department of Physics, Guelph ON (Canada); Kanungo, R. [Saint Mary' s University, Department of Astronomy and Physics, Halifax NS (Canada); Petrache, C.M. [Universite Paris-Saclay, CSNSM, CNRS-IN2P3, Orsay Cedex (France); Wang, Z.M. [Simon Fraser University, Department of Chemistry, Burnaby BC (Canada); TRIUMF, Vancouver BC (Canada); Wood, J.L. [Georgia Institute of Technology, School of Physics, Atlanta, GA (United States); Yates, S.W. [University of Kentucky, Departments of Chemistry and Physics and Astronomy, Lexington, KY (United States)
2017-02-15
The {sup 116}Sn nucleus contains a collective rotational band originating from proton π 2p-2h excitations across the proton Z = 50 shell gap. Even though this nucleus has been extensively investigated in the past, there was still missing information on the low-energy interband transitions connecting the intruder and normal structures. The low-lying structure of {sup 116}Sn was investigated through a high-statistics study of the β{sup -} decay of {sup 116m1}In with the 8π spectrometer and its ancillary detectors at TRIUMF. These measurements are critical in order to properly characterize the π 2p-2h rotational band. Weak γ-decay branches are observed utilizing γ-γ coincidence spectroscopy methods, leading to the first direct observation of the 85 keV 2{sub 2}{sup +} → 0{sub 3}{sup +} γ ray with a transition strength of B(E2) = 99.7(84) W.u. The analysis of these results strongly suggests that the 2027 keV 0{sub 3}{sup +} state should replace the previously assigned 1757 keV 0{sub 2}{sup +} state as the band-head of the π 2p-2h rotational band. (orig.)
Baryons from quantum mechanics on the Lie group u(3)
Trinhammer, Ole L
2011-01-01
We develop a hamiltonian framework on the Lie group u(3), which we call allospace and which is supposed to carry all the colour dynamics needed to describe the baryon spectrum. The energy eigenstates of our particular Schr\\"odinger equation tends to predict realistically all certain baryon resonances in the NDelta sector. The grouping and number of resonances is predicted by the model from a single fitting of the ground state N(939). The Hamiltonian also contains terms from the group space Laplacian to take care of the superimposed hypercharge and isospin flavour structure. Scarce neutral flavour singlet resonances are predicted and may show up around 4500 MeV in neutron diffraction dissociation experiments above the threshold in the free charm system Sigmacplus(2455)Dminus . We give a controversial prediction of the neutron-proton mass difference as originating in a period doubling of certain parametric states. The group space dynamics communicates with real space via the exterior derivative which projects o...
Entanglement routers using macroscopic singlets.
Bayat, Abolfazl; Bose, Sougato; Sodano, Pasquale
2010-10-29
We propose a mechanism where high entanglement between very distant boundary spins is generated by suddenly connecting two long Kondo spin chains. We show that this procedure provides an efficient way to route entanglement between multiple distant sites. We observe that the key features of the entanglement dynamics of the composite spin chain are well described by a simple model of two singlets, each formed by two spins. The proposed routing mechanism is a footprint of the emergence of a Kondo cloud in a Kondo system and can be engineered and observed in varied physical settings.
Verschuere, B.; Spruyt, A.; Meijer, E.H.; Otgaar, H.
2011-01-01
Brain imaging studies suggest that truth telling constitutes the default of the human brain and that lying involves intentional suppression of the predominant truth response. By manipulating the truth proportion in the Sheffield lie test, we investigated whether the dominance of the truth response i
Verschuere, B.; Spruyt, A.; Meijer, E.H.; Otgaar, H.
2011-01-01
Brain imaging studies suggest that truth telling constitutes the default of the human brain and that lying involves intentional suppression of the predominant truth response. By manipulating the truth proportion in the Sheffield lie test, we investigated whether the dominance of the truth response
Vermillion, Marti
1985-01-01
Lying is a symptom of a much broader problem. Primary motivations are need for acceptance, fear of punishment, and desire for attention. Children learn about honesty through observation, both directly and indirectly. Admitting mistakes, especially to children, is invaluable and can help break the lying syndrome. (MT)
Medicine, lies and deceptions.
Benn, P
2001-04-01
This article offers a qualified defence of the view that there is a moral difference between telling lies to one's patients, and deceiving them without lying. However, I take issue with certain arguments offered by Jennifer Jackson in support of the same conclusion. In particular, I challenge her claim that to deny that there is such a moral difference makes sense only within a utilitarian framework, and I cast doubt on the aptness of some of her examples of non-lying deception. But I argue that lies have a greater tendency to damage trust than does non-lying deception, and suggest that since many doctors do believe there is a moral boundary between the two types of deception, encouraging them to violate that boundary may have adverse general effects on their moral sensibilities.
Color Singlet Production at NNLO in MCFM
Energy Technology Data Exchange (ETDEWEB)
Boughezal, Radja [Argonne; Campbell, John M. [Fermilab; Ellis, R. Keith [Durham U., IPPP; Focke, Christfried [Northwestern U.; Giele, Walter [Fermilab; Liu, Xiaohui [Maryland U.; Petriello, Frank [Northwestern U.; Williams, Ciaran [SUNY, Buffalo
2016-05-25
We present the implementation of several color-singlet final-state processes at Next-to-Next-to Leading Order (NNLO) accuracy in QCD to the publicly available parton-level Monte Carlo program MCFM. Specifically we discuss the processes $pp\\rightarrow H$, $pp\\rightarrow Z$, $pp\\rightarrow W$, $pp\\rightarrow HZ$, $pp\\rightarrow HW$ and $pp\\rightarrow\\gamma\\gamma$. Decays of the unstable bosons are fully included, resulting in a flexible fully differential Monte Carlo code. The NNLO corrections have been calculated using the non-local $N$-jettiness subtraction approach. Special attention is given to the numerical aspects of running MCFM for these processes at this order. We pay particular attention to the systematic uncertainties due to the power corrections induced by the $N$-jettiness regularization scheme and the evaluation time needed to run the hybrid openMP/MPI version of MCFM at NNLO on multi-processor systems.
Dependence of nuclear spin singlet lifetimes on RF spin-locking power
DeVience, Stephen J; Rosen, Matthew S
2012-01-01
We measure the lifetime of long-lived nuclear spin singlet states as a function of the strength of the RF spin-locking field and present a simple theoretical model that agrees well with our measurements, including the low-RF-power regime. We also measure the lifetime of a long-lived coherence between singlet and triplet states that does not require a spin-locking field for preservation. Our results indicate that for many molecules, singlet states can be created using weak RF spin-locking fields: more than two orders of magnitude lower RF power than in previous studies. Our findings suggest that in many biomolecules, singlets and related states with enhanced lifetimes might be achievable in vivo with safe levels of RF power.
Evasive Lying in Strategic Communication
Khalmetski, Kiryl; Rockenbach, Bettina; Werner, Peter
2017-01-01
In a sender-receiver game we investigate if sanctions for lying induce more truth-telling. Senders may not only choose between truth-telling and (explicit) lying, but may also engage in evasive lying by credibly pretending not to know. Sanctions promote truth-telling if senders cannot engage in evasive lying. If evasive lying is possible, explicit lying is largely substituted by evasive lying, in line with the notion that evasive lying is perceived as sufficiently less psychologically costly.
Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
Directory of Open Access Journals (Sweden)
Javier Morales
Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.
Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study
Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else
2012-01-01
Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966
Mukhopadhyay, Indra
2016-07-01
This paper reports the analysis of the high resolution (0.0019 cm-1) Fourier transform infrared (FTIR) spectrum for asymmetrically deuterated methanol CHD2OH (methanol-D2) at a low temperature for the CD2 wagging band for the lowest lying trans-species (e0). In spite of the complexity and perturbation in the spectra, assignments were possible for the CD2 wagging band for a maximum K value of 10. In total, about 500 spectral lines have been assigned. Analysis of the spectral lines has been performed in terms of state dependent molecular parameters, Q-branch origins and asymmetry splitting. Assignments have been thoroughly confirmed using combination relations (see text). The catalogue of the assigned transition wavenumbers will help identification and prediction of far infrared (FIR) optically pumped CO2 lasers. The absorption lines close to the several 10R and 10P CO2 laser lines have also been identified. These should help experimentalists to optimize the power of the emission FIR laser lines and to predict new lines and should prove valuable as a laboratory support for interstellar detection in "Radio Astronomy". To our knowledge this is the first time such vibrational infrared (IR) high resolution study in CHD2OH is being performed.
Bakhurst, D
1992-06-01
This article challenges Jennifer Jackson's recent defence of doctors' rights to deceive patients. Jackson maintains there is a general moral difference between lying and intentional deception: while doctors have a prima facie duty not to lie, there is no such obligation to avoid deception. This paper argues 1) that an examination of cases shows that lying and deception are often morally equivalent, and 2) that Jackson's position is premised on a species of moral functionalism that misconstrues the nature of moral obligation. Against Jackson, it is argued that both lying and intentional deception are wrong where they infringe a patient's right to autonomy or his/her right to be treated with dignity. These rights represent 'deontological constraints' on action, defining what we must not do whatever the functional value of the consequences. Medical ethics must recognise such constraints if it is to contribute to the moral integrity of medical practice.
Iachello, Francesco
2015-01-01
This course-based primer provides an introduction to Lie algebras and some of their applications to the spectroscopy of molecules, atoms, nuclei and hadrons. In the first part, it concisely presents the basic concepts of Lie algebras, their representations and their invariants. The second part includes a description of how Lie algebras are used in practice in the treatment of bosonic and fermionic systems. Physical applications considered include rotations and vibrations of molecules (vibron model), collective modes in nuclei (interacting boson model), the atomic shell model, the nuclear shell model, and the quark model of hadrons. One of the key concepts in the application of Lie algebraic methods in physics, that of spectrum generating algebras and their associated dynamic symmetries, is also discussed. The book highlights a number of examples that help to illustrate the abstract algebraic definitions and includes a summary of many formulas of practical interest, such as the eigenvalues of Casimir operators...
Additive Lie (ζ-Lie) Derivations and Generalized Lie (ζ-Lie)Derivations on Prime Algebras
Institute of Scientific and Technical Information of China (English)
Xiao Fei QI; Jin Chuan HOU
2013-01-01
The additive (generalized) ζ-Lie derivations on prime algebras are characterized.It is shown,under some suitable assumptions,that an additive map L is an additive generalized Lie derivation if and only if it is the sum of an additive generalized derivation and an additive map from the algebra into its center vanishing all commutators; is an additive (generalized) ζ-Lie derivation with ζ ≠ 1 if and only if it is an additive (generalized) derivation satisfying L(ζA) =ζL(A) for all A.These results are then used to characterize additive (generalized) ζ-Lie derivations on several operator algebras such as Banach space standard operator algebras and von Neumman algebras.
Lying, honor, and contradiction
National Research Council Canada - National Science Library
Michael Gilsenan
2016-01-01
.... +Superscript 1 -Superscript With a particular concentration on the manifold practices of what will be called "lying," I shall try to show the way in which individuals in a Lebanese village negotiate...
The Higgs mass derived from the U(3) Lie group
Trinhammer, Ole L; Jensen, Mogens Stibius
2015-01-01
The Higgs mass value is derived from a Hamiltonian on the Lie group U(3) where we relate strong and electroweak energy scales. The baryon states of nucleon and delta resonances originate in specific Bloch wave degrees of freedom coupled to a Higgs mechanism which also gives rise to the usual gauge boson masses. The derived Higgs mass is around 125 GeV. From the same Hamiltonian we derive the relative neutron to proton mass ratio. All compare rather well with the experimental values. We predict scarce neutral flavour baryon singlets that should be visible in scattering cross sections for negative pions on protons, in photoproduction on neutrons, in neutron diffraction dissociation experiments and in invariant mass spectra of protons and negative pions in B-decays. The fundamental predictions are based on just one length scale and the fine structure constant. More particular predictions rely also on the weak mixing angle and the up-down quark flavour mixing matrix element. With differential forms on the measure...
Singlet exciton fission in polycrystalline pentacene: from photophysics toward devices.
Wilson, Mark W B; Rao, Akshay; Ehrler, Bruno; Friend, Richard H
2013-06-18
Singlet exciton fission is the process in conjugated organic molecules bywhich a photogenerated singlet exciton couples to a nearby chromophore in the ground state, creating a pair of triplet excitons. Researchers first reported this phenomenon in the 1960s, an event that sparked further studies in the following decade. These investigations used fluorescence spectroscopy to establish that exciton fission occurred in single crystals of several acenes. However, research interest has been recently rekindled by the possibility that singlet fission could be used as a carrier multiplication technique to enhance the efficiency of photovoltaic cells. The most successful architecture to-date involves sensitizing a red-absorbing photoactive layer with a blue-absorbing material that undergoes fission, thereby generating additional photocurrent from higher-energy photons. The quest for improved solar cells has spurred a drive to better understand the fission process, which has received timely aid from modern techniques for time-resolved spectroscopy, quantum chemistry, and small-molecule device fabrication. However, the consensus interpretation of the initial studies using ultrafast transient absorption spectroscopy was that exciton fission was suppressed in polycrystalline thin films of pentacene, a material that would be otherwise expected to be an ideal model system, as well as a viable candidate for fission-sensitized photovoltaic devices. In this Account, we review the results of our recent transient absorption and device-based studies of polycrystalline pentacene. We address the controversy surrounding the assignment of spectroscopic features in transient absorption data, and illustrate how a consistent interpretation is possible. This work underpins our conclusion that singlet fission in pentacene is extraordinarily rapid (∼80 fs) and is thus the dominant decay channel for the photoexcited singlet exciton. Further, we discuss our demonstration that triplet excitons
Casida, Mark E.; Jamorski, Christine; Casida, Kim C.; Salahub, Dennis R.
1998-03-01
This paper presents an evaluation of the performance of time-dependent density-functional response theory (TD-DFRT) for the calculation of high-lying bound electronic excitation energies of molecules. TD-DFRT excitation energies are reported for a large number of states for each of four molecules: N2, CO, CH2O, and C2H4. In contrast to the good results obtained for low-lying states within the time-dependent local density approximation (TDLDA), there is a marked deterioration of the results for high-lying bound states. This is manifested as a collapse of the states above the TDLDA ionization threshold, which is at -ɛHOMOLDA (the negative of the highest occupied molecular orbital energy in the LDA). The -ɛHOMOLDA is much lower than the true ionization potential because the LDA exchange-correlation potential has the wrong asymptotic behavior. For this reason, the excitation energies were also calculated using the asymptotically correct potential of van Leeuwen and Baerends (LB94) in the self-consistent field step. This was found to correct the collapse of the high-lying states that was observed with the LDA. Nevertheless, further improvement of the functional is desirable. For low-lying states the asymptotic behavior of the exchange-correlation potential is not critical and the LDA potential does remarkably well. We propose criteria delineating for which states the TDLDA can be expected to be used without serious impact from the incorrect asymptotic behavior of the LDA potential.
Energy Technology Data Exchange (ETDEWEB)
Cohen, Timothy; /SLAC /Michigan U., MCTP; Kearney, John; Pierce, Aaron; /Michigan U., MCTP; Tucker-Smith, David; /Williams Coll.
2012-02-15
In light of recent data from direct detection experiments and the Large Hadron Collider, we explore models of dark matter in which an SU(2){sub L} doublet is mixed with a Standard Model singlet. We impose a thermal history. If the new particles are fermions, this model is already constrained due to null results from XENON100. We comment on remaining regions of parameter space and assess prospects for future discovery. We do the same for the model where the new particles are scalars, which at present is less constrained. Much of the remaining parameter space for both models will be probed by the next generation of direct detection experiments. For the fermion model, DeepCore may also play an important role.
Singlet and triplet instability theorems
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.
Photochemical Dynamics of Intramolecular Singlet Fission
Lin, Zhou; Iwasaki, Hikari; Van Voorhis, Troy
2017-06-01
Singlet fission (SF) converts a singlet exciton (S_1) into a pair of triplet ones (T_1) via a ``multi-exciton'' (ME) intermediate: S_1 \\longleftrightarrow ^1ME \\longleftrightarrow ^1(T_1T_1) \\longrightarrow 2T_1. In exothermic cases, e.g., crystalline pentacene or its derivatives, the quantum yield of SF can reach 200%. With SF doubling the electric current generated by an incident high-energy photon, the solar conversion efficiency in pentacene-based organic photovoltaics (OPVs) can exceed the Shockley-Queisser limit of 33.7%. The ME state is popularly considered to be a dimeric state with significant charge transfer (CT) character that is strongly coupled to both S_1 and ^1(T_1T_1), while this local model lacks strong support from full quantum dynamics studies. Intramolecular SF (ISF) occurring to covalently-bound dimers in the solution phase is an excellent model for a straightforward dynamics simulation of local excitons. In the present study, we investigate the ISF mechanisms for three covalently-bound dimers of pentacene derivatives, including ortho-, meta-, and para-bis(6,13-bis(triisopropylsilylethynyl)pentacene)benzene, in non-protic solvents. Specifically, we propagate the real-time, non-adiabatic quantum mechanical/molecular mechanical (QM/MM) dynamics on the potential energy surfaces associated with the states of S_1, ^1(T_1T_1) and CT. We explore how the energies of these ISF-relevant states and the non-adiabatic couplings between each other fluctuate with time and the instantaneous molecular configuration (e.g., intermonomer distance and orientation). We also quantitatively compare Condon and non-Condon ISF dynamics with solution-phase spectroscopic data. Our results allow us to understand the roles of CT energy levels in the ISF mechanism and propose a design strategy to maximize ISF efficiency. M. B. Smith and J. Michl, Chem. Rev. 110, 6891 (2010). W. Shockley and H. J. Queisser, J. Appl. Phys. 32, 510 (1961). T. C. Berkelbach, M. S. Hybertsen
Müller, Holger S. P.; Drouin, B. J.; Pearson, J. C.; Brown, L. R.; Kleiner, I.; Sams, R. L.
2010-06-01
Methyl cyanide, CH_3CN, is an important interstellar molecule, in particular in hot and dense molecular cores, and it may play a role in the atmospheres of planets or of Titan. Therefore, we have recorded extensive rotational and rovibrational spectra up to ˜ 1.6 THz and ˜ 1500 cm-1, respectively. The present investigation extends our analysis of states with v_8 ≤ 2 at vibrational energies below 740 cm-1 and takes into consideration findings from an analysis of the ν _4 band and the higher-lying ν _7 (at ˜1042 cm-1) and 3ν _8 ^1 (at ˜1078 cm-1) bands. The rotational data extend to J = 87 and K = 15, infrared assignments currently extend to 55 and 12, respectively. Parameters affecting only v_7 = 1 or v_8 = 3 as well as some additional interaction parameters were kept fixed to values from (b). The largest perturbations of v_4 = 1 are caused by a Δ k = 0, Δ l = 3 interaction with v_8 = 3 at K = 8. Despite the inclusion of the interaction parameter and a centrifugal distortion correction, residuals amount to more than 200 MHz very close to the resonance. Removal of these residuals probably requires explicit inclusion of v_8 = 3 data. Several additional perturbations exist at lower as well as higher K with v_8 = 2, v_7 = 1 and v_8 = 3. Higher values of K are difficult to reproduce in spite of an extensive set of distortion parameters which, at highest orders, have rather large magnitudes, possibly indicating unaccounted interactions which would probably occur with states even higher than v_8 = 3. H. S. P. Müller et al., contribution WG03, presented at the 62nd International Symposium on Molecular Spectroscopy, June 18-22, 2007, Columbus, Ohio, USA. A.-M. Tolonen et al., J. Mol. Spectrosc. 160 (1993) 554-565.
Park, G Barratt; Field, Robert W
2016-01-01
The $\\mathrm{\\tilde{C}}$ $^1$B$_2$ state of SO$_2$ has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. The asymmetry in the potential energy surface is expressed as a staggering in the energy levels of the $\
Seron, X
2014-10-01
The issue of lying occurs in neuropsychology especially when examinations are conducted in a forensic context. When a subject intentionally either presents non-existent deficits or exaggerates their severity to obtain financial or material compensation, this behaviour is termed malingering. Malingering is discussed in the general framework of lying in psychology, and the different procedures used by neuropsychologists to evidence a lack of collaboration at examination are briefly presented and discussed. When a lack of collaboration is observed, specific emphasis is placed on the difficulty in unambiguously establishing that this results from the patient's voluntary decision.
Singlet oxygen-mediated damage to proteins and its consequences
DEFF Research Database (Denmark)
Davies, Michael Jonathan
2003-01-01
on the identification of reactive peroxide intermediates formed on Tyr, His, and Trp residues is discussed. These peroxides may be important propagating species in protein oxidation as they can initiate further oxidation via both radical and non-radical reactions. Such processes can result in the transmittal of damage......Proteins comprise approximately 68% of the dry weight of cells and tissues and are therefore potentially major targets for oxidative damage. Two major types of processes can occur during the exposure of proteins to UV or visible light. The first of these involves direct photo-oxidation arising from...... the absorption of UV radiation by the protein, or bound chromophore groups, thereby generating excited states (singlet or triplets) or radicals via photo-ionisation. The second major process involves indirect oxidation of the protein via the formation and subsequent reactions of singlet oxygen generated...
Purification of an unpolarized spin ensemble into entangled singlet pairs
Greiner, Johannes N; Wrachtrup, Jörg
2016-01-01
Dynamical polarization of nuclear spin ensembles is of central importance for magnetic resonance studies, precision sensing and for applications in quantum information theory. Here we propose a scheme to generate long-lived singlet pairs in an unpolarized nuclear spin ensemble which is dipolar coupled to the electron spins of a Nitrogen Vacancy center in diamond. The quantum mechanical back-action induced by frequent spin-selective readout of the NV centers allows the nuclear spins to pair up into maximally entangled singlet pairs. Counterintuitively, the robustness of the pair formation to dephasing noise improves with increasing size of the spin ensemble. We also show how the paired nuclear spin state allows for enhanced sensing capabilities of NV centers in diamond.
Indian Academy of Sciences (India)
A K Pulhani; M L Shah; G P Gupta; B M Suri
2010-12-01
Spectrally resolved laser-induced fluorescence technique was used to uniquely assign total angular momentum () values to high-lying even-parity energy levels of atomic samarium. Unique value assignment was done for seven energy levels in the energy region 34,800–36,200 cm-1 , recently observed and reported in the literature.
Müller, Holger S. P.; Ordu, Matthias H.; Lewen, Frank; Brown, Linda; Drouin, Brian; Pearson, John; Sung, Keeyoon; Kleiner, Isabelle; Sams, Robert
2015-06-01
Rotational and rovibrational spectra of methyl cyanide were recorded to analyze interactions in low-lying vibrational states and to construct line lists for radio astronomical observations as well as for infrared spectroscopic investigations of planetary atmospheres. The rotational spectra cover large portions of the 36-1627~GHz region. In the infrared (IR), a spectrum was recorded for this study in the region of 2ν_8 around 717~cm-1 with assignments covering 684-765~cm-1. Additional spectra in the ν _8 region were used to validate the analysis. Using ν _8 data as well as spectroscopic parameters for v_4 = 1, v_7 = 1, and v_8 = 3 from previous studies, we analyzed rotational data involving v = 0, v_8 = 1, and v_8 = 2 up to high J and K quantum numbers. We analyzed a strong Δ v_8 = ± 1, Δ K = 0, Δ l = ±3 Fermi resonance between v_8 = 1-1 and v_8 = 2+2 at K = 14 and obtained preliminary results for two further Fermi resonances between v_8 = 2 and 3. We also found resonant Δ v_8 = ± 1, Δ K = ∓ 2, Δ l = ± 1 interactions between v_8 = 1 and 2 and present the first detailed analysis of such a resonance between v_8 = 0 and 1. We discuss the impact of this analysis on the v_8 = 1 and 2 as well as on the axial v = 0 parameters and compare selected CH_3CN parameters with those of CH_3CCH and CH_3NC. We evaluated transition dipole moments of ν _8, 2ν _8 - ν _8, and 2ν _8 for remote sensing in the IR. Part of this work was carried out at the Jet Propulsion Laboratory under contract with the National Aeronautics and Space Administration. M. Koivusaari et al., J. Mol. Spectrosc. 152 (1992) 377-388. A.-M. Tolonen et al., J. Mol. Spectrosc. 160 (1993) 554-565.
Interference effects of two scalar boson propagators on the LHC search for the singlet fermion DM
Ko, P
2016-01-01
A gauge invariant UV-completion for singlet fermion DM interacting with the standard model (SM) particles involves a new singlet scalar. Therefore the model contains two scalar mediators, mixtures of the SM Higgs boson and a singlet scalar boson. Collider phenomenology of the interference effect between these two scalar propagators is studied in this work. This interference effect can be either constructive or destructive in the DM production cross section depending on both singlet scalar and DM masses, and it will soften the final state jets in the full mass region. Applying the CMS mono-jet search to our model, we find the interference effect plays a very important role in the DM search sensitivity, and the DM production cross section of our model is more than one order of magnitude below the LHC sensitivity at current stage.
Interference effects of two scalar boson propagators on the LHC search for the singlet fermion DM
Ko, P.; Li, Jinmian
2017-02-01
A gauge invariant UV-completion for singlet fermion DM interacting with the standard model (SM) particles involves a new singlet scalar. Therefore the model contains two scalar mediators, mixtures of the SM Higgs boson and a singlet scalar boson. Collider phenomenology of the interference effect between these two scalar propagators is studied in this work. This interference effect can be either constructive or destructive in the DM production cross section depending on both singlet scalar and DM masses, and it will soften the final state jets in the full mass region. Applying the CMS mono-jet search to our model, we find the interference effect plays a very important role in the DM search sensitivity, and the DM production cross section of our model is more than one order of magnitude below the LHC sensitivity at current stage.
Energy Technology Data Exchange (ETDEWEB)
Joffe, David Noah
2004-12-01
The author presents the results of a search for the spin-singlet P-wave state h{sub c}(1{sup 1}P{sub 1}) of charmonium formed through proton-antiproton annihilation at Fermilab experiment E835. The decay channels which were studied were p{bar p} {yields} J/{psi} + X {yields} e{sup +}e{sup -} + X, p{bar p} {yields} J/{psi} + {pi}{sup 0} {yields} e{sup +}e{sup -} + {gamma}{gamma}, p{bar p} {yields} J/{psi} + {pi}{sup 0}{pi}{sup 0} {yields} e{sup +}e{sup -} + 4{gamma}, and the neutral channel p{bar p} {yields} {eta}{sub c}{gamma} {yields} ({gamma}{gamma}){gamma}. The decay p{bar p} {yields} J/{psi}{gamma} {yields} e{sup +}e{sup -}{gamma}, into which {sup 1}P{sub 1} decay is forbidden by C-parity conservation, was also examined for comparison. The 90% confidence upper limits for the decay channels studied in the mass range 3525.1-3527.3 MeV for a {sup 1}P{sub 1} resonance with a presumed width of 1.0 MeV were determined to be B(p{bar p} {yields} {sup 1}P{sub 1}) x B({sup 1}P{sub 1} {yields} J/{psi} + X) {le} 1.8 x 10{sup -7}, B(p{bar p} {yields} {sup 1}P{sub 1}) x B({sup 1}P{sub 1} {yields} J/{psi} + {pi}{sup 0}) {le} 1.2 x 10{sup -7}, and B(p{bar p} {yields} {sup 1}P{sub 1}) x B({sup 1}P{sub 1} {yields} J/{psi}{gamma}) {le} 1.0 x 10{sup -7}. No evidence for a {sup 1}P{sub 1} enhancement was observed in either of the two additional reactions studied; p{bar p} {yields} J/{psi} + {pi}{sup 0}{pi}{sup 0} {yields} e{sup +}e{sup -} + 4{gamma} and p{bar p} {yields} {eta}{sub c}{gamma} {yields} ({gamma}{gamma}){gamma}.
Energy Technology Data Exchange (ETDEWEB)
Joffe, David Noah [Northwestern Univ., Evanston, IL (United States)
2004-12-01
The author presents the results of a search for the spin-singlet P-wave state h_{c}(1^{1} P_{1}) of charmonium formed through proton-antiproton annihilation at Fermilab experiment E835. The decay channels which were studied were p$\\bar{p}$ → J/Ψ + X → e^{+}e^{-} + X, p$\\bar{p}$ → J/Ψ + π^{0} → e^{+}e^{-} + γγ, p$\\bar{p}$ → J/Ψ + π^{0}π^{0} → e^{+}e^{-} + 4γ, and the neutral channel p$\\bar{p}$ → η_{c}γ → (γγ)γ. The decay p$\\bar{p}$ → J/Ψγ → e^{+}e^{-}γ, into which ^{1}P_{1} decay is forbidden by C-parity conservation, was also examined for comparison. The 90% confidence upper limits for the decay channels studied in the mass range 3525.1-3527.3 MeV for a ^{1}P_{1} resonance with a presumed width of 1.0 MeV were determined to be B(p$\\bar{p}$ → ^{1}P_{1}) x B(^{1}P_{1} → J/Ψ + X) ≤ 1.8 x 10^{-7}, B(p$\\bar{p}$ → ^{1}P_{1}) x B(^{1}P_{1} → J/Ψ + π^{0}) ≤ 1.2 x 10^{-7}, and B(p$\\bar{p}$ → ^{1}P_{1}) x B(^{1}P_{1} → J/Ψγ) ≤ 1.0 x 10^{-7}. No evidence for a ^{1}P_{1} enhancement was observed in either of the two additional reactions studied; p$\\bar{p}$ → J/Ψ + π^{0}π^{0} → e^{+}e^{-} + 4γ and p$\\bar{p}$ → η_{c}γ → (γγ)γ.
H. van Ditmarsch (Hans); D.J.N. van Eijck (Jan); F.A.G. Sietsma (Floor); Y. Wang (Yanjing); D.J.N. van Eijck (Jan); R. Verbrugge
2011-01-01
htmlabstractWe look at lying as an act of communication, where (i) the proposition that is communicated is not true, (ii) the utterer of the lie knows (or believes) that what she communicates is not true, and (iii) the utterer of the lie intends the lie to be taken as truth. Rather than dwell on
A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers
2016-08-24
acscentsci.6b00063 ACS Cent. Sci. 2016, 2, 316−324 This is an open access article published under an ACS AuthorChoice License, which permits copying and...and correspond to the ground state gg, the ME state, tt, the two singlet LE states, eg and ge, the two CT states, ac and ca, and the doubly excited...singlet fission (τiSF) and the rate of triplet pair (2×T1) recombination (τrec). ACS Central Science Research Article DOI: 10.1021/acscentsci.6b00063
Lie algebraic noncommutative gravity
Banerjee, Rabin; Mukherjee, Pradip; Samanta, Saurav
2007-06-01
We exploit the Seiberg-Witten map technique to formulate the theory of gravity defined on a Lie algebraic noncommutative space-time. Detailed expressions of the Seiberg-Witten maps for the gauge parameters, gauge potentials, and the field strengths have been worked out. Our results demonstrate that notwithstanding the introduction of more general noncommutative structure there is no first order correction, exactly as happens for a canonical (i.e. constant) noncommutativity.
Introduction to quantum Lie algebras
Delius, G W
1996-01-01
Quantum Lie algebras are generalizations of Lie algebras whose structure constants are power series in h. They are derived from the quantized enveloping algebras \\uqg. The quantum Lie bracket satisfies a generalization of antisymmetry. Representations of quantum Lie algebras are defined in terms of a generalized commutator. In this paper the recent general results about quantum Lie algebras are introduced with the help of the explicit example of (sl_2)_h.
Lie groups, lie algebras, and representations an elementary introduction
Hall, Brian
2015-01-01
This textbook treats Lie groups, Lie algebras and their representations in an elementary but fully rigorous fashion requiring minimal prerequisites. In particular, the theory of matrix Lie groups and their Lie algebras is developed using only linear algebra, and more motivation and intuition for proofs is provided than in most classic texts on the subject. In addition to its accessible treatment of the basic theory of Lie groups and Lie algebras, the book is also noteworthy for including: a treatment of the Baker–Campbell–Hausdorff formula and its use in place of the Frobenius theorem to establish deeper results about the relationship between Lie groups and Lie algebras motivation for the machinery of roots, weights and the Weyl group via a concrete and detailed exposition of the representation theory of sl(3;C) an unconventional definition of semisimplicity that allows for a rapid development of the structure theory of semisimple Lie algebras a self-contained construction of the representations of compac...
Exciton Correlations in Intramolecular Singlet Fission.
Sanders, Samuel N; Kumarasamy, Elango; Pun, Andrew B; Appavoo, Kannatassen; Steigerwald, Michael L; Campos, Luis M; Sfeir, Matthew Y
2016-06-15
We have synthesized a series of asymmetric pentacene-tetracene heterodimers with a variable-length conjugated bridge that undergo fast and efficient intramolecular singlet fission (iSF). These compounds have distinct singlet and triplet energies, which allow us to study the spatial dynamics of excitons during the iSF process, including the significant role of exciton correlations in promoting triplet pair generation and recombination. We demonstrate that the primary photoexcitations in conjugated dimers are delocalized singlets that enable fast and efficient iSF. However, in these asymmetric dimers, the singlet becomes more localized on the lower energy unit as the length of the bridge is increased, slowing down iSF relative to analogous symmetric dimers. We resolve the recombination kinetics of the inequivalent triplets produced via iSF, and find that they primarily decay via concerted processes. By identifying different decay channels, including delayed fluorescence via triplet-triplet annihilation, we can separate transient species corresponding to both correlated triplet pairs and uncorrelated triplets. Recombination of the triplet pair proceeds rapidly despite our experimental and theoretical demonstration that individual triplets are highly localized and unable to be transported across the conjugated linker. In this class of compounds, the rate of formation and yield of uncorrelated triplets increases with bridge length. Overall, these constrained, asymmetric systems provide a unique platform to isolate and study transient species essential for singlet fission, which are otherwise difficult to observe in symmetric dimers or condensed phases.
Lie algebraic Noncommutative Gravity
Banerjee, R; Samanta, S; Banerjee, Rabin; Mukherjee, Pradip; Samanta, Saurav
2007-01-01
The minimal (unimodular) formulation of noncommutative general relativity, based on gauging the Poincare group, is extended to a general Lie algebra valued noncommutative structure. We exploit the Seiberg -- Witten map technique to formulate the theory as a perturbative Lagrangian theory. Detailed expressions of the Seiberg -- Witten maps for the gauge parameters, gauge potentials and the field strengths have been worked out. Our results demonstrate that notwithstanding the introduction of more general noncommutative structure there is no first order correction, exactly as happens for a canonical (i.e. constant) noncommutativity.
Energy Technology Data Exchange (ETDEWEB)
NONE
1996-02-01
The Department of Energy has prepared an Environmental Assessment (DOE/EA-1143) evaluating the construction, equipping and operation of the proposed Lied Transplant Center at the University of Nebraska Medical Center in Omaha, Nebraska. Based on the analysis in the EA, the DOE has determined that the proposed action does not constitute a major federal action significantly affecting the quality of the human environment within the meaning of the National Environmental Policy Act of 1969 (NEPA). Therefore, the preparation of an Environmental Statement in not required.
Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production
Energy Technology Data Exchange (ETDEWEB)
Yoshii, Hiroshi, E-mail: yoshii@nirs.go.jp [Research Center for Radiation Emergency Medicine, National Institute of Radiological Science, Chiba 263-8555 (Japan); Faculty of Medical Sciences, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Yoshii, Yukie, E-mail: yukiey@nirs.go.jp [Molecular Imaging Center, National Institute of Radiological Science, Chiba 263-8555 (Japan); Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Asai, Tatsuya [Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Faculty of Engineering, University of Fukui, Fukui 910-8507 (Japan); Furukawa, Takako [Molecular Imaging Center, National Institute of Radiological Science, Chiba 263-8555 (Japan); Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Takaichi, Shinichi [Department of Biology, Nippon Medical School, Kawasaki, Kanagawa 211-0063 (Japan); Fujibayashi, Yasuhisa [Molecular Imaging Center, National Institute of Radiological Science, Chiba 263-8555 (Japan); Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan)
2012-01-06
Highlights: Black-Right-Pointing-Pointer Some photo-excited carotenoids have photosensitizing ability. Black-Right-Pointing-Pointer They are able to produce ROS. Black-Right-Pointing-Pointer Photo-excited fucoxanthin can produce singlet oxygen through energy transfer. -- Abstract: Carotenoids, natural pigments widely distributed in algae and plants, have a conjugated double bond system. Their excitation energies are correlated with conjugation length. We hypothesized that carotenoids whose energy states are above the singlet excited state of oxygen (singlet oxygen) would possess photosensitizing properties. Here, we demonstrated that human skin melanoma (A375) cells are damaged through the photo-excitation of several carotenoids (neoxanthin, fucoxanthin and siphonaxanthin). In contrast, photo-excitation of carotenoids that possess energy states below that of singlet oxygen, such as {beta}-carotene, lutein, loroxanthin and violaxanthin, did not enhance cell death. Production of reactive oxygen species (ROS) by photo-excited fucoxanthin or neoxanthin was confirmed using a reporter assay for ROS production with HeLa Hyper cells, which express a fluorescent indicator protein for intracellular ROS. Fucoxanthin and neoxanthin also showed high cellular penetration and retention. Electron spin resonance spectra using 2,2,6,6-tetramethil-4-piperidone as a singlet oxygen trapping agent demonstrated that singlet oxygen was produced via energy transfer from photo-excited fucoxanthin to oxygen molecules. These results suggest that carotenoids such as fucoxanthin, which are capable of singlet oxygen production through photo-excitation and show good penetration and retention in target cells, are useful as photosensitizers in photodynamic therapy for skin disease.
Police lie detection accuracy: the effect of lie scenario.
O'Sullivan, Maureen; Frank, Mark G; Hurley, Carolyn M; Tiwana, Jaspreet
2009-12-01
Although most people are not better than chance in detecting deception, some groups of police professionals have demonstrated significant lie detection accuracy. One reason for this difference may be that the types of lies police are asked to judge in scientific experiments often do not represent the types of lies they see in their profession. Across 23 studies, involving 31 different police groups in eight countries, police officers tested with lie detection scenarios using high stakes lies (i.e., the lie was personally involving and/or resulted in substantial rewards or punishments for the liar) were significantly more accurate than law enforcement officials tested with low stakes lies. Face validity and construct validity of various lie scenarios are differentiated.
Yao, J M
2016-01-01
We present a generator-coordinate calculation, based on a relativistic energy-density functional, of the low-lying spectra in the isotopes $^{150}$Nd and $^{150}$Sm and of the nuclear matrix element that governs the neutrinoless double-beta decay of the first isotope to the second. We carefully examine the impact of octupole correlations on both nuclear structure and the double-beta decay matrix element. Octupole correlations turn out to reduce quadrupole collectivity in both nuclei. Shape fluctuations, however, dilute the effects of octupole deformation on the double-beta decay matrix element, so that the overall octupole-induced quenching is only about 7\\%.
Detection prospects of singlet fermionic dark matter
Esch, Sonja; Yaguna, Carlos E
2013-01-01
A singlet fermion which interacts only with a new singlet scalar provides a viable and minimal scenario that can explain the dark matter. The singlet fermion is the dark matter particle whereas the new scalar mixes with the Higgs boson providing a link between the dark matter sector and the Standard Model. In this paper, we present an updated analysis of this model focused on its detection prospects. Both, the parity-conserving case and the most general case are considered. First, the full parameter space of the model is analyzed, and the regions compatible with the dark matter constraint are obtained and characterized. Then, the implications of current and future direct detection experiments are taken into account. Specifically, we determine the regions of the multidimensional parameter space that are currently excluded and those that are going to be probed by next generation experiments. Finally, indirect detection prospects are discussed and the expected signal at neutrino telescopes is calculated.
Detection prospects of singlet fermionic dark matter
Esch, Sonja; Klasen, Michael; Yaguna, Carlos E.
2013-10-01
A singlet fermion which interacts only with a new singlet scalar provides a viable and minimal scenario that can explain the dark matter. The singlet fermion is the dark matter particle whereas the new scalar mixes with the Higgs boson providing a link between the dark matter sector and the standard model. In this paper, we present an updated analysis of this model focused on its detection prospects. Both the parity-conserving case and the most general case are considered. First, the full parameter space of the model is analyzed, and the regions compatible with the dark matter constraint are obtained and characterized. Then, the implications of current and future direct detection experiments are taken into account. Specifically, we determine the regions of the multidimensional parameter space that are currently excluded and those that are going to be probed by next generation experiments. Finally, indirect detection prospects are discussed and the expected signal at neutrino telescopes is calculated.
Dean, Jacob C; Zhang, Ruomeng; Hallani, Rawad K; Pensack, Ryan D; Sanders, Samuel N; Oblinsky, Daniel G; Parkin, Sean R; Campos, Luis M; Anthony, John E; Scholes, Gregory D
2017-08-30
Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of >5000 cm(-1). Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result
Dean, Jacob C.
2017-08-18
Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of >5000 cm−1. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result
[Diagnostic imaging of lying].
Lass, Piotr; Sławek, Jarosław; Sitek, Emilia; Szurowska, Edyta; Zimmermann, Agnieszka
2013-01-01
Functional diagnostic imaging has been applied in neuropsychology for more than two decades. Nowadays, the functional magnetic resonance (fMRI) seems to be the most important technique. Brain imaging in lying has been performed and discussed since 2001. There are postulates to use fMRI for forensic purposes, as well as commercially, e.g. testing the loyalty of employees, especially because of the limitations of traditional polygraph in some cases. In USA fMRI is performed in truthfulness/lying assessment by at least two commercial companies. Those applications are a matter of heated debate of practitioners, lawyers and specialists of ethics. The opponents of fMRI use for forensic purposes indicate the lack of common agreement on it and the lack of wide recognition and insufficient standardisation. Therefore it cannot serve as a forensic proof, yet. However, considering the development of MRI and a high failure rate of traditional polygraphy, forensic applications of MRI seem to be highly probable in future.
Telling Lies: The Irrepressible Truth?
Williams, Emma J.; Bott, Lewis A.; Patrick, John; Lewis, Michael B.
2013-01-01
Telling a lie takes longer than telling the truth but precisely why remains uncertain. We investigated two processes suggested to increase response times, namely the decision to lie and the construction of a lie response. In Experiments 1 and 2, participants were directed or chose whether to lie or tell the truth. A colored square was presented and participants had to name either the true color of the square or lie about it by claiming it was a different color. In both experiments we found that there was a greater difference between lying and telling the truth when participants were directed to lie compared to when they chose to lie. In Experiments 3 and 4, we compared response times when participants had only one possible lie option to a choice of two or three possible options. There was a greater lying latency effect when questions involved more than one possible lie response. Experiment 5 examined response choice mechanisms through the manipulation of lie plausibility. Overall, results demonstrate several distinct mechanisms that contribute to additional processing requirements when individuals tell a lie. PMID:23573277
Group discussion improves lie detection
National Research Council Canada - National Science Library
Nadav Klein; Nicholas Epley
2015-01-01
... identify when a person is lying. These experiments demonstrate that the group advantage in lie detection comes through the process of group discussion, and is not a product of aggregating individual opinions...
Lying because we care: Compassion increases prosocial lying.
Lupoli, Matthew J; Jampol, Lily; Oveis, Christopher
2017-07-01
Prosocial lies, or lies intended to benefit others, are ubiquitous behaviors that have important social and economic consequences. Though emotions play a central role in many forms of prosocial behavior, no work has investigated how emotions influence behavior when one has the opportunity to tell a prosocial lie-a situation that presents a conflict between two prosocial ethics: lying to prevent harm to another, and honesty, which might also provide benefits to the target of the lie. Here, we examine whether the emotion of compassion influences prosocial lying, and find that compassion causally increases and positively predicts prosocial lying. In Studies 1 and 2, participants evaluated a poorly written essay and provided feedback to the essay writer. Experimentally induced compassion felt toward the essay writer (Study 1) and individual differences in trait compassion (Study 2) were positively associated with inflated feedback to the essay writer. In both of these studies, the relationship between compassion and prosocial lying was partially mediated by an enhanced importance placed on preventing emotional harm. In Study 3, we found moderation such that experimentally induced compassion increased lies that resulted in financial gains for a charity, but not lies that produced financial gains for the self. This research illuminates the emotional underpinnings of the common yet morally complex behavior of prosocial lying, and builds on work highlighting the potentially harmful effects of compassion-an emotion typically seen as socially beneficial. (PsycINFO Database Record (c) 2017 APA, all rights reserved).
Gbur, Peter; Dedic, Roman; Chorvat, Dusan; Miskovsky, Pavol; Hala, Jan; Jancura, Daniel
2009-01-01
Time-resolved fluorescence and phosphorescence study of hypericin (Hyp) in complex with low-density lipoproteins (LDL) as well as the evolution of singlet oxygen formation and annihilation after illumination of Hyp/LDL complexes at room temperature are presented in this work. The observed shortening of the fluorescence lifetime of Hyp at high Hyp/LDL molar ratios (>25:1) proves the self-quenching of the excited singlet state of monomeric Hyp at these concentration ratios. The very short lifetime ( approximately 0.5 ns) of Hyp fluorescence at very high Hyp/LDL ratios (>150:1) suggests that at high local Hyp concentration inside LDL molecules fast and ultrafast nonradiative decay processes from excited singlet state of Hyp become more important. Contrary to the lifetime of the singlet excited state, the lifetime (its shorter component) of Hyp phosphorescence is not dependent on Hyp/LDL ratio in the studied concentration range. The amount of singlet oxygen produced as well as the integral intensity of Hyp phosphorescence after illumination of Hyp/LDL complexes resemble the dependence of the concentration of molecules of Hyp in monomeric state on Hyp/LDL until a concentration ratio of 60:1. This fact confirms that only monomeric Hyp is able to produce the excited triplet state of Hyp, which in aerobic conditions leads to singlet oxygen production. The value of singlet oxygen lifetime ( approximately 8 micros) after its formation from the excited triplet state of Hyp in LDL proves that molecules of singlet oxygen remain for a certain period of time inside LDL particles and are not immediately released to the aqueous surrounding. That Hyp exists in the complex with LDL in the monodeprotonated state is also demonstrated.
H. van Ditmarsch (Hans); D.J.N. van Eijck (Jan); F.A.G. Sietsma (Floor)
2012-01-01
textabstractWe model lying as a communicative act changing the beliefs of the agents in a multi-agent system. With Augustine, we see lying as an utterance believed to be false by the speaker and uttered with the intent to deceive the addressee. The deceit is successful if the lie is believed
Debey, E.; De Houwer, J.; Verschuere, B.
2014-01-01
Cognitive models of deception focus on the conflict-inducing nature of the truth activation during lying. Here we tested the counterintuitive hypothesis that the truth can also serve a functional role in the act of lying. More specifically, we examined whether the construction of a lie can involve a
Debey, E.; De Houwer, J.; Verschuere, B.
2014-01-01
Cognitive models of deception focus on the conflict-inducing nature of the truth activation during lying. Here we tested the counterintuitive hypothesis that the truth can also serve a functional role in the act of lying. More specifically, we examined whether the construction of a lie can involve a
Dotsenko, V.; Shadrin, S.; Vallette, B.
2016-01-01
In this paper, we develop the deformation theory controlled by pre-Lie algebras; the main tool is a new integration theory for preLie algebras. The main field of application lies in homotopy algebra structures over a Koszul operad; in this case, we provide a homotopical description of the associated
Singlet aided infinite resource reduction in the comparison of distant fields
Bose, S; Plenio, M B
2001-01-01
We present a task which can be faithfully solved with finite resources only when aided by particles prepared in a particular entangled state: the singlet state. The task consists of identifying the mutual parallelity or orthogonality of weak distant magnetic fields whose absolute directions are completely unknown.
Goldfield, Evelyn M.; Kirby, Kate P.
1987-01-01
Configuration interaction wave functions, potential energy curves, and dipole moment functions have been calculated for the four lowest 3Sigma(-) and the three lowest 3Pi states and 5Sigma(-) states of NH. The electronic wave functions were constructed to give a balanced description of valence-Rydberg interactions. Two repulsive states have been identified as important photodissociation pathways. Spectroscopic constants are presented for the bound states, and results are compared to other theoretical and experimental work. The possible predissociation of the A 3Pi state by the 1 5Sigma(-) state is discussed.
Goldfield, Evelyn M.; Kirby, Kate P.
1987-01-01
Configuration interaction wave functions, potential energy curves, and dipole moment functions have been calculated for the four lowest 3Sigma(-) and the three lowest 3Pi states and 5Sigma(-) states of NH. The electronic wave functions were constructed to give a balanced description of valence-Rydberg interactions. Two repulsive states have been identified as important photodissociation pathways. Spectroscopic constants are presented for the bound states, and results are compared to other theoretical and experimental work. The possible predissociation of the A 3Pi state by the 1 5Sigma(-) state is discussed.
Quantization on nilpotent Lie groups
Fischer, Veronique
2016-01-01
This book presents a consistent development of the Kohn-Nirenberg type global quantization theory in the setting of graded nilpotent Lie groups in terms of their representations. It contains a detailed exposition of related background topics on homogeneous Lie groups, nilpotent Lie groups, and the analysis of Rockland operators on graded Lie groups together with their associated Sobolev spaces. For the specific example of the Heisenberg group the theory is illustrated in detail. In addition, the book features a brief account of the corresponding quantization theory in the setting of compact Lie groups. The monograph is the winner of the 2014 Ferran Sunyer i Balaguer Prize.
Involvement of singlet oxygen in biochemical systems
Energy Technology Data Exchange (ETDEWEB)
Singh, A. (Whiteshell Nuclear Research Establishment, Pinawa, Manitoba, Canada); Singh, H.; Kremers, W.; Koroll, G.W.
1981-01-01
Reliable monitoring of singlet oxygen in biological systems is complicated by reactions of superoxide anions and hydroxyl radicals, which can often be present. However, tryptophan is now emerging as a potential monitor of singlet oxygen and other reactive oxy-species, in aqueous solutions, on the basis of the following results. Tryptophan reacts with singlet oxygen to produce N-form lykynurenine (FK), kynurenine (K), 2-carboxy-3a hydroxy-1,2,3,3a,8,8a-hexahydropyrrlo-(2,3b)-indole (HPI) and an unidentified product. It also reacts with hydroxyl radicals; in the presence of oxygen, six products are formed which include 5-hydroxy-tryptophan, FK, K, and HPI; in the absence of oxygen, K and HPI are not formed and a different unidentified product is formed. The relative yields of the common products in these three cases are different. Trytophan does not react with superoxide anions. Thus, by comparing the products formed and their ratios, tyrptophan can be used as a discriminating monitor for singlet oxygen, superoxide anions and hydroxyl radicals. On direct irradiation of tryptophan, at 280 nm, only two products (FK and HPI) are formed in measurable yields. In reaction with high concentrations of hydrogen peroxide, seven products result. Again, the relative ratios of the common products in these cases are different than the ones described above. In radiolysis, in the absence of oxygen, the decomposition of tryptophan is negligible. (JMT)
Size of colour singlets in QCD jets
Bertolini, S.; Marchesini, G.
1982-11-01
By using the jet calculus technique, the size of the colour singlet clusters of emitted partons of mass Q0 is estimated. For α(Q20)/πapplications of preconfinement in pertubbative QCD. This result is very sensitive to the correct treatment of infrared singularities. Permanent address: Istituto di Fisica, Università di Parma, Parma, Italy.
Recycling and imaging of nuclear singlet hyperpolarization
DEFF Research Database (Denmark)
Pileio, Giuseppe; Bowen, Sean; Laustsen, Christoffer
2013-01-01
observation of the same batch of polarized nuclei over a period of 30 min and more. We report a recycling protocol in which the enhanced nuclear polarization achieved by dissolution-DNP is observed with full intensity and then returned to singlet order. MRI experiments may be run on a portion of the available...
Singlet oxygen generation in PUVA therapy studied using electronic structure calculations
Energy Technology Data Exchange (ETDEWEB)
Serrano-Perez, Juan Jose; Olaso-Gonzalez, Gloria; Merchan, Manuela [Instituto de Ciencia Molecular, Universitat de Valencia, Apartado 22085, ES-46071 Valencia (Spain); Serrano-Andres, Luis, E-mail: Luis.Serrano@uv.es [Instituto de Ciencia Molecular, Universitat de Valencia, Apartado 22085, ES-46071 Valencia (Spain)
2009-06-12
The ability of furocoumarins to participate in the PUVA (Psoralen + UV-A) therapy against skin disorders and some types of cancer, is analyzed on quantum chemical grounds. The efficiency of the process relies on its capability to populate its lowest triplet excited state, and then either form adducts with thymine which interfere DNA replication or transfer its energy, generating singlet molecular oxygen damaging the cell membrane in photoactivated tissues. By determining the spin-orbit couplings, shown to be the key property, in the intersystem crossing yielding the triplet state of the furocoumarin, the electronic couplings in the triplet-triplet energy transfer process producing the singlet oxygen, and the reaction rates and lifetimes, the efficiency in the phototherapeutic action of the furocoumarin family is predicted as: khellin < 5-methoxypsoralen (5-MOP) < 8-methoxypsoralen (8-MOP) < psoralen < 4,5',8-trimethylpsoralen (TMP) < 3-carbethoxypsoralen (3-CPS), the latter being the most efficient photosensitizer and singlet oxygen generator.
Entanglement and Metrology with Singlet-Triplet Qubits
Shulman, Michael Dean
Electron spins confined in semiconductor quantum dots are emerging as a promising system to study quantum information science and to perform sensitive metrology. Their weak interaction with the environment leads to long coherence times and robust storage for quantum information, and the intrinsic tunability of semiconductors allows for controllable operations, initialization, and readout of their quantum state. These spin qubits are also promising candidates for the building block for a scalable quantum information processor due to their prospects for scalability and miniaturization. However, several obstacles limit the performance of quantum information experiments in these systems. For example, the weak coupling to the environment makes inter-qubit operations challenging, and a fluctuating nuclear magnetic field limits the performance of single-qubit operations. The focus of this thesis will be several experiments which address some of the outstanding problems in semiconductor spin qubits, in particular, singlet-triplet (S-T0) qubits. We use these qubits to probe both the electric field and magnetic field noise that limit the performance of these qubits. The magnetic noise bath is probed with high bandwidth and precision using novel techniques borrowed from the field of Hamiltonian learning, which are effective due to the rapid control and readout available in S-T 0 qubits. These findings allow us to effectively undo the undesired effects of the fluctuating nuclear magnetic field by tracking them in real-time, and we demonstrate a 30-fold improvement in the coherence time T2*. We probe the voltage noise environment of the qubit using coherent qubit oscillations, which is partially enabled by control of the nuclear magnetic field. We find that the voltage noise bath is frequency-dependent, even at frequencies as high as 1MHz, and it shows surprising and, as of yet, unexplained temperature dependence. We leverage this knowledge of the voltage noise environment, the
Radiative neutrino masses in the singlet-doublet fermion dark matter model with scalar singlets
Restrepo, Diego; Sánchez-Peláez, Marta; Zapata, Oscar; Tangarife, Walter
2015-01-01
When the singlet-doublet fermion dark matter model is extended with additional $Z_2$--odd real singlet scalars, neutrino masses and mixings can be generated at one-loop level. In this work, we discuss the salient features arising from the combination of the two resulting simplified dark matter models. When the $Z_2$-lightest odd particle is a scalar singlet, $\\operatorname{Br}(\\mu\\to e \\gamma)$ could be measurable provided that the singlet-doublet fermion mixing is small enough. In this scenario, also the new decay channels of vector-like fermions into scalars can generate interesting leptonic plus missing transverse energy signals at the LHC. On the other hand, in the case of doublet-like fermion dark matter, scalar coannihilations lead to an increase in the relic density which allow to lower the bound of doublet-like fermion dark matter.
Hu, Weifeng
2015-01-01
We describe and extend the formalism of state-specific analytic density matrix renormalization group (DMRG) energy gradients, first used by Liu et al (J. Chem. Theor.Comput. 9, 4462 (2013)). We introduce a DMRG wavefunction maximum overlap following technique to facilitate state-specific DMRG excited state optimization. Using DMRG configuration interaction (DMRG-CI) gradients we relax the low-lying singlet states of a series of trans-polyenes up to C20H22. Using the relaxed excited state geometries as well as correlation functions, we elucidate the exciton, soliton, and bimagnon ("single-fission") character of the excited states, and find evidence for a planar conical intersection.
Knippenberg, Stefan; Starcke, Jan-Hendrik; Wormit, Michael; Dreuw, Andreas
2010-01-01
Abstract The vertical excited electronic states of linearly fused neutral polyacenes and their radical cations have been investigated using the algebraic diagrammatic construction scheme of sec- ond order (ADC(2)). While strict ADC(2) (ADC(2)-s) correctly reproduces trends for mainly singly excited states, in extended ADC(2) (ADC(2)-x) the description of doubly excited states is critically improved. It is shown that a combined application of strict and extended ADC(2) nicely reveal...
Lie Subalgebras in a Certain Operator Lie Algebra with Involution
Institute of Scientific and Technical Information of China (English)
Shan Li SUN; Xue Feng MA
2011-01-01
We show in a certain Lie'-algebra,the connections between the Lie subalgebra G+:＝G+G*+[G,G*],generated by a Lie subalgebra G,and the properties of G.This allows us to investigate some useful information about the structure of such two Lie subalgebras.Some results on the relations between the two Lie subalgebras are obtained.As an application,we get the following conclusion:Let A (∪) B(X)be a space of self-adjoint operators and L:＝A ⊕ iA the corresponding complex Lie*-algebra.G+＝G+G*+[G,G*]and G are two LM-decomposable Lie subalgebras of,L with the decomposition G+＝R(G+)+S,G＝RG+SG,and RG (∪) R(C+).Then G+ is ideally finite iff RG+:＝RG+RG*+[RG,RG*]is a quasisolvable Lie subalgebra,SG+:＝SG+SG*+[SG,SG*]is an ideally finite semisimple Lie subalgebra,and [RG,SG]＝[RG*,SG]＝{0}.
Nakhate, S. G.; Mukund, Sheo; Bhattacharyya, Soumen
2017-02-01
Rotationally resolved excitation spectra of TaN molecules, produced in a free-jet, have been studied using laser-induced fluorescence spectroscopy. Thirteen excited electronic states in the energy region, 23,500-30,000 cm-1 have been observed. The molecular constants, Ω-quantum numbers and radiative lifetimes have been determined for these states. Because of the case (c) behavior and absence of the regular energy spacing, the assignments of the excited electronic states of TaN become difficult. The number of observed excited electronic states is significantly larger than currently predicted, indicated a need for additional ab initio calculations.
Energy Technology Data Exchange (ETDEWEB)
Dedic, R.; Svoboda, A.; Psencik, J.; Lupinkova, L.; Komenda, J.; Hala, J. E-mail: hala@karlov.mff.cuni.cz
2003-05-01
Singlet oxygen generated via chlorophyll triplets in photosynthetic systems can destroy basic components of photosynthetic apparatus. In order to study this process a sensitive spectroscopic experimental set-up was built to detect both weak infrared (IR) chlorophyll phosphorescence (between 900 and 1000 nm) and singlet oxygen phosphorescence (at 1270 nm). The spectral and time resolution of the used monochromator and photon counting multiscaler are sufficient to provide two-dimensional matrix of temporally and spectrally resolved IR luminescence data. We have studied IR emission of photosystem II particles in D{sub 2}O and H{sub 2}O buffer including the effect of the sodium dodecyl sulphate (SDS) detergent. Both sub-microsecond lifetime of chlorophyll triplet states and microsecond lifetime of singlet oxygen were determined. The singlet oxygen lifetime in D{sub 2}O (of 18 {mu}s) was approximately five times longer than that in H{sub 2}O. Quantum efficiency of singlet oxygen generation in photosystem II particles was significantly lower than that in chlorophyll a in acetone, however, it could be substantially increased by addition of SDS.
750 GeV diphoton resonance from singlets in an exceptional supersymmetric standard model
Energy Technology Data Exchange (ETDEWEB)
King, Stephen F. [Physics and Astronomy, University of Southampton,SO17 1BJ Southampton (United Kingdom); Nevzorov, Roman [ARC Centre of Excellence for Particle Physics at the Terascale,Department of Physics, The University of Adelaide,Adelaide, South Australia 5005 (Australia)
2016-03-21
The 750–760 GeV diphoton resonance may be identified as one or two scalars and/or one or two pseudoscalars contained in the two singlet superfields S{sub 1,2} arising from the three 27-dimensional representations of E{sub 6}. The three 27s also contain three copies of colour-triplet charge ∓1/3 vector-like fermions D,D̄ and two copies of charged inert Higgsinos H̃{sup +},H̃{sup −} to which the singlets S{sub 1,2} may couple. We propose a variant of the E{sub 6}SSM where the third singlet S{sub 3} breaks a gauged U(1){sub N} above the TeV scale, predicting Z{sub N}{sup ′}, D,D̄, H̃{sup +},H̃{sup −} at LHC Run 2, leaving the two lighter singlets S{sub 1,2} with masses around 750 GeV. We calculate the branching ratios and cross-sections for the two scalar and two pseudoscalar states associated with the S{sub 1,2} singlets, including possible degeneracies and maximal mixing, subject to the constraint that their couplings remain perturbative up to the unification scale.
Lie groups and automorphic forms
Ji, Lizhen; Xu, H W; Yau, Shing-Tung
2006-01-01
Lie groups are fundamental objects in mathematics. They occur naturally in differential geometry, algebraic geometry, representation theory, number theory, and other areas. Closely related are arithmetic subgroups, locally symmetric spaces and the spectral theory of automorphic forms. This book consists of five chapters which give comprehensive introductions to Lie groups, Lie algebras, arithmetic groups and reduction theories, cohomology of arithmetic groups, and the Petersson and Kuznetsov trace formulas.
Demonstration of entanglement of electrostatically coupled singlet-triplet qubits.
Shulman, M D; Dial, O E; Harvey, S P; Bluhm, H; Umansky, V; Yacoby, A
2012-04-13
Quantum computers have the potential to solve certain problems faster than classical computers. To exploit their power, it is necessary to perform interqubit operations and generate entangled states. Spin qubits are a promising candidate for implementing a quantum processor because of their potential for scalability and miniaturization. However, their weak interactions with the environment, which lead to their long coherence times, make interqubit operations challenging. We performed a controlled two-qubit operation between singlet-triplet qubits using a dynamically decoupled sequence that maintains the two-qubit coupling while decoupling each qubit from its fluctuating environment. Using state tomography, we measured the full density matrix of the system and determined the concurrence and the fidelity of the generated state, providing proof of entanglement.
Device-independent parallel self-testing of two singlets
Wu, Xingyao; Bancal, Jean-Daniel; McKague, Matthew; Scarani, Valerio
2016-06-01
Device-independent self-testing offers the possibility of certifying the quantum state and measurements, up to local isometries, using only the statistics observed by querying uncharacterized local devices. In this paper we study parallel self-testing of two maximally entangled pairs of qubits; in particular, the local tensor product structure is not assumed but derived. We prove two criteria that achieve the desired result: a double use of the Clauser-Horne-Shimony-Holt inequality and the 3 ×3 magic square game. This demonstrate that the magic square game can only be perfectly won by measuring a two-singlet state. The tolerance to noise is well within reach of state-of-the-art experiments.
Bosonization and Lie Group Structure
Ha, Yuan K
2015-01-01
We introduce a concise quantum operator formula for bosonization in which the Lie group structure appears in a natural way. The connection between fermions and bosons is found to be exactly the connection between Lie group elements and the group parameters. Bosonization is an extraordinary way of expressing the equation of motion of a complex fermion field in terms of a real scalar boson in two dimensions. All the properties of the fermion field theory are known to be preserved under this remarkable transformation with substantial simplification and elucidation of the original theory, much like Lie groups can be studied by their Lie algebras.
Debey, Evelyne; De Houwer, Jan; Verschuere, Bruno
2014-09-01
Cognitive models of deception focus on the conflict-inducing nature of the truth activation during lying. Here we tested the counterintuitive hypothesis that the truth can also serve a functional role in the act of lying. More specifically, we examined whether the construction of a lie can involve a two-step process, where the first step entails activating the truth, based upon which a lie response can be formulated in a second step. To investigate this hypothesis, we tried to capture the covert truth activation in a reaction-time based deception paradigm. Together with each question, we presented either the truth or lie response as distractors. If lying depends on the covert activation of the truth, deceptive responses would thus be facilitated by truth distractors relative to lie distractors. Our results indeed revealed such a "covert congruency" effect, both in errors and reaction times (Experiment 1). Moreover, stimulating participants to use the distractor information by increasing the proportion of truth distractor trials enlarged the "covert congruency" effects, and as such confirmed that the effects operate at a covert response level (Experiment 2). Our findings lend support to the idea that lying relies on a first step of truth telling, and call for a shift in theoretical thinking that highlights both the functional and interfering properties of the truth activation in the lying process. Copyright © 2014 Elsevier B.V. All rights reserved.
Differential geometry on Lie groups
2013-01-01
Resumo: Neste trabalho estudamos os aspectos geométricos dos grupos de Lie do ponto de vista da geometria Riemanniana, geometria Hermitiana e geometria Kähler, através das estruturas geométricas invariantes associadas. Exploramos resultados relacionados às curvaturas da variedade Riemanniana subjacente a um grupo de Lie através do estudo de sua álgebra de Lie correspondente. No contexto da geometria Hermitiana e geometria Kähler, para um caso concreto de grupo de Lie complexo, investigaram su...
Affective Priming Caused by Lying
Directory of Open Access Journals (Sweden)
Megumi Sato
2011-10-01
Full Text Available Typically, arousal increases when telling a lie, as indicated in psychophysiological studies about lie detection. But the emotional valence induced by lying is unknown, though intuition indicates that it may be negative. Indeed, the Electrodermal Activity (EDA, used in such studies, only shows arousal changes during an emotional response. In this study, we examined the emotional valence induced by lying using two tasks. First, in the deceptive task, participants answered “no” to every question regarding the nature of displayed playing cards. Therefore, they told a lie about specific cards. During the task, their EDA was recorded. Secondly, in the figure estimation task, they assessed pictures by “like” or “dislike” after looking at playing cards visibly or subliminally as prime stimuli. We expected them to tend to estimate figures by “dislike” when cards relevant to deception were previously shown. This would mean that an affective priming effect due to telling a lie happened. Actually, this effect was found only when prime stimuli were displayed visibly. This result suggests that lying per se induces negative emotions even without motivation or punishment due to lying. Furthermore, we found that such effect was more blatant in participants whose EDA changes were salient while lying.
Xie, Daiqian; Guo, Hua; Peterson, Kirk A.
2001-12-01
Accurate ab initio potential-energy surfaces of the 3A2 and 3B1 states of ozone and their nonadiabatic coupling are reported near the ground-state equilibrium geometry using an internally contracted multireference configuration interaction method. These coupled three-dimensional potential-energy surfaces enable the first theoretical characterization of all three vibrational modes in the Wulf band. Reasonably good agreement with recent experimental observations is obtained.
Venter, G J; Meiswinkel, R
1994-12-01
Altogether 52 078 Culicoides biting midges of 35 species were collected during February 1990 and 1993 in 40 light-trap collections made on 17 cattle and/or sheep farms in the Bethlehem and Fouriesburg districts of the colder, high-lying eastern Orange Free State. Culicoides (Avaritia) bolitinos was by far the most abundant species, representing 50.9% of all specimens collected. Culicoides (A.) imicola, considered to be the most common stock-associated species in the summer rainfall areas of southern Africa, and the only proven vector of bluetongue virus (BTV) and African horsesickness virus (AHSV) in the subregion, was uncommon, comprising only 1.4%. While AHS is apparently absent, BT and bovine ephemeral fever (BEF) are endemic in this cooler, high-lying area of South Africa. The virtual absence of C. imicola implies that other Culicoides species, such as C. bolitinos and C. cornutus, may be involved in transmitting BT virus (and perhaps BEF) in the eastern Orange Free State, and possibly elsewhere in Africa. Virus isolation attempts made on 45 single species pools of C. bolitinos, C. pycnostictus, C. milnei, C. leucostictus, C. zuluensis and C. gulbenkiani were, however, negative. Finally, 20 of 28 blood-engorged Culicoides of 11 species, which were tested against cattle, sheep, horse, pig and bird antisera, tested only positive against cattle antisera.
Theatres of the lie: 'crazy' deception and lying as drama.
Dongen, Els van
2002-08-01
In this article, the author argues that lying is drama, theatre, which brings about transition, reflection, reversal and involvement of the participants in the drama. By means of ethnographic data of a psychiatric ward, the author shows that lying of mental patients is not pathological, but a ritual of affliction. By using Turner's theory about rituals and performance and Goffman's theory about presentation of the self it will be showed that lying serves the redefinition of reciprocity and solidarity. With the help of Bakhtin's work on Rabelais, the author discusses the nature of the drama of the lie. It is concluded that a perspective on lying as theatre may be of use outside psychiatric wards and will occur in imbalanced power relationships.
Neutrino Masses and Scalar Singlet Dark Matter
Bhattacharya, Subhaditya; Nandi, S
2016-01-01
We propose a simple extension of the Standard Model (SM) which has a viable dark matter (DM) candidate, as well as can explain the generation of tiny neutrino masses. The DM is an electroweak (EW) singlet scalar $S$, odd under an imposed exact $Z_2$ symmetry, interacting to SM through `Higgs-portal' coupling, while all other particles are even under $Z_2$. The model also has an EW isospin $3/2$ scalar, $\\Delta$ and a pair of EW isospin vector, $\\Sigma$ and $\\bar{\\Sigma}$, responsible for generating tiny neutrino mass via the effective dimension seven operator. Thanks to the additional interactions with $\\Delta$, the scalar singlet DM $S$ survives a large region of parameter space by relic density constraints from WMAP/PLANCK and direct search bounds from updated LUX data. Constraints on the model from Large Hadron Collider (LHC) has also been discussed.
Neutrino masses and scalar singlet dark matter
Bhattacharya, Subhaditya; Jana, Sudip; Nandi, S.
2017-03-01
We propose a simple extension of the Standard Model (SM) which has a viable dark matter (DM) candidate and can explain the generation of tiny neutrino masses. The DM is an electroweak (EW) singlet scalar S , odd under an imposed exact Z2 symmetry, that interacts with the SM through the "Higgs portal" coupling, while all other particles are even under Z2. The model also has an EW isospin 3 /2 scalar Δ and a pair of EW isospin vectors Σ and Σ ¯, which are responsible for generating tiny neutrino mass via the effective dimension-seven operator. Thanks to the additional interactions with Δ , the scalar singlet DM S survives a large region of parameter space by relic density constraints from WMAP/Planck and direct search bounds from updated LUX data. Constraints on the model from the LHC are also discussed.
Photosensitized production of singlet oxygen: spatially-resolved optical studies in single cells
DEFF Research Database (Denmark)
Breitenbach, Thomas; Kuimova, Marina; Gbur, Peter;
2009-01-01
be monitored using viability assays. Time- and spatially-resolved optical measurements of both singlet oxygen and its precursor, the excited state sensitizer, reflect the complex and dynamic morphology of the cell. These experiments help elucidate photoinduced, oxygen-dependent events that compromise cell...
Storage of magnetization as singlet order by optimal control designed pulses
DEFF Research Database (Denmark)
Laustsen, Christoffer; Bowen, Sean; Vinding, Mads Sloth
2014-01-01
. With this aim, optimal control theory was applied to create pulses that for near‐equivalent spins accomplish transfers in and out of the singlet state with maximum efficiency while ensuring robustness toward variations in the nuclear spin system Hamiltonian (chemical shift, J‐couplings, B1 and B magnetic field...
Arsenault, D. L.; Tokaryk, D. W.; Adam, A. G.; Linton, C.
2016-06-01
We have taken laser-induced fluorescence spectra of jet-cooled nickel monofluoride formed in a laser-ablation molecular beam source. Dispersed-fluorescence spectroscopy confirms predictions by Hougen (2011) that the parity assignments of levels in the Ω = 1 / 2 state 1570 cm-1 above the ground state should be reversed from those given in Krouti et al. (2002). The quality of the high-resolution spectra was sufficient to measure the [22.9]1.5-X1.5 band for five isotopologues of nickel and the [22.9]1.5-[0.25]0.5 band for molecules containing 58Ni and 60Ni. The spectral line positions for each isotopologue were fit to the Hamiltonian model given by Hougen, which was extended to allow for calculation of the parity-splitting parameter in the ground state.
Helicity Evolution at Small $x$: Flavor Singlet and Non-Singlet Observables
Kovchegov, Yuri V; Sievert, Matthew D
2016-01-01
We extend our earlier results for the quark helicity evolution at small $x$ to derive the small-$x$ asymptotics of the flavor singlet and flavor non-singlet quark helicity TMDs and PDFs and of the $g_1$ structure function. In the flavor singlet case we re-derive the evolution equations obtained in our previous paper on the subject, performing additional cross-checks of our results. In the flavor non-singlet case we construct new small-$x$ evolution equations by employing the large-$N_c$ limit. All evolution equations resum double-logarithmic powers of $\\alpha_s \\, \\ln^2 (1/x)$ in the polarization-dependent evolution along with the single-logarithmic powers of $\\alpha_s \\, \\ln (1/x)$ in the unpolarized evolution which includes saturation effects. We solve the linearized flavor non-singlet equation analytically, obtaining an intercept which agrees with the one calculated earlier by Bartels, Ermolaev and Ryskin using the infra-red evolution equations. Our numerical solution of the linearized large-$N_c$ evolutio...
Allis, D. G.; Fedor, A. M.; Korter, T. M.; Bjarnason, J. E.; Brown, E. R.
2007-06-01
The narrow terahertz (THz) features in crystalline biotin and lactose monohydrate observed in recent experimental studies are considered by solid-state density functional theory (DFT) calculations. The lowest-frequency THz features in both solid-state biotin and lactose monohydrate are assigned to external hindered rotational modes and not to the lowest-frequency internal modes predicted from isolated-molecule calculations. The motions of the molecules associated with these narrow THz features and the interactions between molecules in the hydrogen-bonded networks of these molecular crystals are discussed, and comparisons are made to similar studies on molecular crystals not exhibiting strong intermolecular interactions.
Deciding isomorphism of Lie algebras
Graaf, W.A. de
2001-01-01
When doing calculations with Lie algebras one of the main problems is to decide whether two given Lie algebras are isomorphic. A partial solution to this problem is obtained by calculating structural invariants. There is also a direct method available which involves the computation of Grobner bases.
The low lying glueball spectrum
Energy Technology Data Exchange (ETDEWEB)
Adam Szczepaniak; Eric Swanson
2003-12-18
The complete low-lying positive charge conjugation glueball spectrum is obtained from QCD. The formalism relies on the construction of an efficient quasiparticle gluon basis for Hamiltonian QCD in Coulomb gauge. The resulting rapidly convergent Fock space expansion is exploited to derive quenched low-lying glueball masses with no free parameters which are in remarkable agreement with lattice gauge theory.
Lie Symmetries of Ishimori Equation
Institute of Scientific and Technical Information of China (English)
SONG Xu-Xia
2013-01-01
The Ishimori equation is one of the most important (2+1)-dimensional integrable models,which is an integrable generalization of (1+1)-dimensional classical continuous Heisenberg ferromagnetic spin equations.Based on importance of Lie symmetries in analysis of differential equations,in this paper,we derive Lie symmetries for the Ishimori equation by Hirota's direct method.
Group discussion improves lie detection.
Klein, Nadav; Epley, Nicholas
2015-06-16
Groups of individuals can sometimes make more accurate judgments than the average individual could make alone. We tested whether this group advantage extends to lie detection, an exceptionally challenging judgment with accuracy rates rarely exceeding chance. In four experiments, we find that groups are consistently more accurate than individuals in distinguishing truths from lies, an effect that comes primarily from an increased ability to correctly identify when a person is lying. These experiments demonstrate that the group advantage in lie detection comes through the process of group discussion, and is not a product of aggregating individual opinions (a "wisdom-of-crowds" effect) or of altering response biases (such as reducing the "truth bias"). Interventions to improve lie detection typically focus on improving individual judgment, a costly and generally ineffective endeavor. Our findings suggest a cheap and simple synergistic approach of enabling group discussion before rendering a judgment.
Biradical vs singlet oxygen photogeneration in suprofen–cholesterol systems
Palumbo, Fabrizio; Bosca, Francisco; Morera, Isabel Maria
2016-01-01
Summary Cholesterol (Ch) is an important lipidic building block and a target for oxidative degradation, which can be induced via free radicals or singlet oxygen (1O2). Suprofen (SP) is a nonsteroidal anti-inflammatory drug that contains the 2-benzoylthiophene (BZT) chromophore and has a π,π* lowest triplet excited state. In the present work, dyads (S)- and (R)-SP-α-Ch (1 and 2), as well as (S)-SP-β-Ch (3) have been prepared from β- or α-Ch and SP to investigate the possible competition between photogeneration of biradicals and 1O2, the key mechanistic steps in Ch photooxidation. Steady-state irradiation of 1 and 2 was performed in dichloromethane, under nitrogen, through Pyrex, using a 400 W medium pressure mercury lamp. The spectral analysis of the separated fractions revealed formation of two photoproducts 4 and 5, respectively. By contrast, under the same conditions, 3 did not give rise to any isolable Ch-derived product. These results point to an intramolecular hydrogen abstraction in 1 and 2 from the C7 position of Ch and subsequent C–C coupling of the generated biradicals. Interestingly, 2 was significantly more photoreactive than 1 indicating a clear stereodifferentiation in the photochemical behavior. Transient absorption spectra obtained for 1–3 were very similar and matched that described for the SP triplet excited state (typical bands with maxima at ca. 350 nm and 600 nm). Direct kinetic analysis of the decay traces at 620 nm led to determination of triplet lifetimes that were ca. 4.1 μs for 1 and 2 and 5.8 μs for 3. From these data, the intramolecular quenching rate constants in 1 and 2 were determined as 0.78 × 105 s−1. The capability of dyads 1–3 to photosensitize the production of singlet oxygen was assessed by time-resolved near infrared emission studies in dichloromethane using perinaphthenone as standard. The quantum yields (ΦΔ) were 0.52 for 1 and 2 and 0.56 for 3. In conclusion, SP-α-Ch dyads are unique in the sense that they
Tran, Van Tan; Tran, Quoc Tri
2016-07-28
The geometrical and electronic structures of VSi3(-/0) clusters have been investigated with the DFT, CCSD(T), and CASSCF/CASPT2 methods. The results showed that the suitable functional to identify the ground states of VSi3(-/0) clusters is not the B3LYP but the BP86. At the BP86, CCSD(T), and CASPT2 levels, the ground state of the anionic cluster was the (1)A' ((1)A1) of tetrahedral η(3)-(Si3)V(-) isomer, while that of the neutral cluster was the 1(2)A' and 1(2)A″ (1(2)E) of the same isomer. The 1(2)A' and 1(2)A″ of the tetrahedral η(3)-(Si3)V isomer were the results of the Jahn-Teller distortions of the 1(2)E in C3v symmetry. All three bands in the photoelectron spectrum of the VSi3(-) cluster were interpreted by one-electron detachments from the (1)A' anionic ground state on the basis of the BP86, CCSD(T), and CASPT2 methods. The calculated adiabatic and vertical detachment energies were in agreement with the experimental values. The broad shape of the first band was explained by Franck-Condon factor simulations for the (1)A' → 1(2)A' and (1)A' → 1(2)A″ transitions within the tetrahedral η(3)-(Si3)V(-/0) isomers.
Prodhan, Suryoday
2016-01-01
Singlet fission is a potential pathway for significant enhancement of efficiency in organic solar cells. In this article, we have studied singlet fission in a pair of polyene molecules employing exact many-body wave packet dynamics. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interaction between them involves transfer terms, intersite electron repulsions and site charge-bond charge repulsion terms. Initial wave packet is constructed from excited singlet state of one molecule and ground state of the other. Time development of this wave packet under the influence of intermolecular interactions is followed within the Schr\\"{o}dinger picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, $2{}^1A$ excited singlet state leads to significant fission yield while the $1{}^1B$ state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, singlet state derived from $1{}^1B$ state also gives si...
Energy Technology Data Exchange (ETDEWEB)
Borisyuk, Petr V.; Vasilyev, Oleg S.; Krasavin, Andrey V.; Troyan, Victor I. [National Research Nuclear University ' ' MEPhI' ' (Moscow Engineering Physics Institute), Kashirskoye shosse 31, 115409 Moscow (Russian Federation); Lebedinskii, Yury Yu. [National Research Nuclear University ' ' MEPhI' ' (Moscow Engineering Physics Institute), Kashirskoye shosse 31, 115409 Moscow (Russian Federation); Moscow Institute of Physics and Technology (State University), Institutskiy per. 9, 141700 Dolgoprudny, Moscow region (Russian Federation); Tkalya, Eugene V. [Skobeltsyn Institute of Nuclear Physics, Lomonosov Moscow State University, Leninskie gory, 119991 Moscow (Russian Federation); Nuclear Safety Institute of Russian Academy of Science, Bol' shaya Tulskaya 52, 115191 Moscow (Russian Federation)
2015-12-15
The results are presented on the study of the electronic structure of thorium atoms adsorbed by the liquid atomic layer deposition from aqueous solution of thorium nitrate on the surface of CaF{sub 2}. The chemical state of the atoms and the change of the band structure in the surface layers of Th/CaF{sub 2} system on CaF{sub 2} substrate were investigated by XPS and REELS techniques. It was found that REELS spectra for Th/CaF{sub 2} system include peaks in the region of low energy losses (3-7 eV) which are missing in the similar spectra for pure CaF{sub 2}. It is concluded that the presence of the observed features in the REELS spectra is associated with the chemical state of thorium atoms and is caused by the presence of uncompensated chemical bonds at the Th/CaF{sub 2} interface, and, therefore, by the presence of unbound 6d- and 7s-electrons of thorium atoms. Assuming the equivalence of the electronic configuration of thorium-229 and thorium-232 atoms, an estimate was made on the time decay of the excited state of thorium-229 nuclei through the channel of the electron conversion. It was found that the relaxation time is about 40 μs for 6d-electrons, and about 1 μs for 7s-electrons. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
Yan, Lingling; Qu, Yizhi; Liu, Chunhua; Wang, Jianguo; Buenker, Robert J
2012-03-28
An ab initio multireference single- and double-excitation configuration interaction (CI) study is carried out for the ground and excited electronic states of alkali-hydride cations (LiH(+), NaH(+), KH(+), RbH(+), and CsH(+)). For all alkali-metal atoms, the first inner-shell and valence electrons (nine active electrons, three for Li) are considered explicitly in the ab initio self-consistent-field and CI calculations. The adiabatic potential energy curves, radial and rotational couplings are calculated and presented. Short-range (∼3 a.u.) potential wells produced by the excitation of the inner-shell electrons are found. The depths of the inner potential wells are much greater than those of the outer wells for the CsH(+) system. The computed spectroscopic constants for the long-range potential well of the 2 (2)Σ(+) state are very close to the available theoretical and experimental data. The electronic states of alkali-hydrogen cations are also compared with each other, it is found that the positions of the potential wells shift to larger internuclear distances gradually, and the depths of these potential wells become greater with increasing alkali-metal atomic number. The relationships between structures of the radial coupling matrix elements and the avoiding crossings of the potential curves are analyzed. From NaH(+) to CsH(+), radial coupling matrix elements display more and more complex structures due to the gradual decrease of energy separations for avoided crossings. Finally, the behavior of some rotational couplings is also shown.
Institute of Scientific and Technical Information of China (English)
ZHANG Jin-Juan; XU Chang; REN Zhong-Zhou
2009-01-01
We present a systematic calculation on the 0c-decay branching ratios to excited-states of an even-even α-decay chain 242Cm→238pu→234U →230Th→226Rn by the improved barrier penetration approach. The changes of the parities between the parent nuclei and the daughter nuclei are properly taken into account. The theoretical values are compared with the available experimental data and the deviation between them is within a factor of 5 in most cases.
Borisyuk, P. V.; Vasilyev, O S; Krasavin, A.V.; Lebedinskii, Yu Yu; V. I. Troyan; Tkalya, E. V.
2015-01-01
The results are presented on the study of the electronic structure of thorium atoms adsorbed by the liquid atomic layer deposition from aqueous solution of thorium nitrate on the surface of CaF2. The chemical state of the atoms and the change of the band structure in the surface layers of Th/CaF2 system on CaF2 substrate were investigated by XPS and REELS techniques. It was found that REELS spectra for Th/CaF2 system include peaks in the region of low energy losses (3-7 eV) which are missing ...
Benshoof, J
1998-01-22
Efforts begun in 1977 as a 1-year project to ensure that Roe vs. Wade was implemented and enforced in the US continue today. Roe recognized that women must have the ability to make autonomous decisions about childbearing in order to be equal participants in society and that the government must remain neutral before the period of fetal viability. This breakthrough in women's rights was quickly threatened by anti-abortion forces that espoused "fetal rights" and demonized women seeking abortion. The 1992 Casey decision, while not overturning Roe, eradicated the key element of state neutrality and reinstated the stereotype that a woman should not be trusted to make an abortion decision on her own. This decision runs counter to court decisions that resist sexual stereotypes in every other area of American life. The latest threat is found in the "partial birth" abortion bans enacted in 17 states and blocked, in most cases, by Federal judges. It is time for the US Supreme Court to abandon sexual stereotypes and recognize that there is no real difference between women who have an abortion and women who choose to give birth.
Detecting true lies: police officers' ability to detect suspects' lies.
Mann, Samantha; Vrij, Aldert; Bull, Ray
2004-02-01
Ninety-nine police officers, not identified in previous research as belonging to groups that are superior in lie detection, attempted to detect truths and lies told by suspects during their videotaped police interviews. Accuracy rates were higher than those typically found in deception research and reached levels similar to those obtained by specialized lie detectors in previous research. Accuracy was positively correlated with perceived experience in interviewing suspects and with mentioning cues to detecting deceit that relate to a suspect's story. Accuracy was negatively correlated with popular stereotypical cues such as gaze aversion and fidgeting. As in previous research, accuracy and confidence were not significantly correlated, but the level of confidence was dependent on whether officers judged actual truths or actual lies and on the method by which confidence was measured.
Lying aversion and prosocial behaviour
Biziou-van-Pol, Laura; Novaro, Arianna; Liberman, Andrés Occhipinti; Capraro, Valerio
2015-01-01
The focus of this paper is the moral conflict between lying aversion and prosociality. What does telling a white lie signal about a person's prosocial tendencies? How does believing a possibly untruthful message signal about a listener's prosocial tendencies? To answer these questions, we conducted a 2x3 experiment. In the first stage we measured altruistic tendencies using a Dictator Game and cooperative tendencies using a Prisoner's dilemma. In the second stage, we used a sender-receiver game to measure aversion to telling a Pareto white lie (i.e., a lie that helps both the liar and the listener), aversion to telling an altruistic white lie (i.e., a lie that helps the listener at the expense of the liar), and skepticism towards believing a possibly untruthful message. We found three major results: (i) both altruism and cooperation are positively correlated with aversion to telling a Pareto white lie; (ii) neither altruism nor cooperation are significantly correlated with aversion to telling an altruistic wh...
Lies, Calculations and Constructions: Beyond How to Lie with Statistics
Best, Joel
2005-01-01
Darrell Huff’s How to Lie with Statistics remains the best-known, nontechnical call for critical thinking about statistics. However, drawing a distinction between statistics and lying ignores the process by which statistics are socially constructed. For instance, bad statistics often are disseminated by sincere, albeit innumerate advocates (e.g., inflated estimates for the number of anorexia deaths) or through research findings selectively highlighted to attract media coverage (e.g., a recent...
Prodhan, Suryoday; Ramasesha, S.
2017-08-01
Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in organic solar cells (OSC). In this paper, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dynamics. In the noninteracting model, the SF yield is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interaction between them involves transfer terms, intersite electron repulsions, and site-charge-bond-charge repulsion terms. Initial wave packet is constructed from excited singlet state of one molecule and ground state of the other. Time development of this wave packet under the influence of intermolecular interactions is followed within the Schrödinger picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, 2 1A excited singlet state leads to significant SF yield while the 1 1B state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient 2 1A character and hence results in significant SF yield. Because of rapid internal conversion, the nature of the lowest excited singlet will determine the SF contribution to OSC efficiency. Furthermore, we find the fission yield depends considerably on the stacking arrangement of the polyene molecules.
Last Multipliers on Lie Algebroids
Indian Academy of Sciences (India)
Mircea Crasmareanu; Cristina-Elena Hreţcanu
2009-06-01
In this paper we extend the theory of last multipliers as solutions of the Liouville’s transport equation to Lie algebroids with their top exterior power as trivial line bundle (previously developed for vector fields and multivectors). We define the notion of exact section and the Liouville equation on Lie algebroids. The aim of the present work is to develop the theory of this extension from the tangent bundle algebroid to a general Lie algebroid (e.g. the set of sections with a prescribed last multiplier is still a Gerstenhaber subalgebra). We present some characterizations of this extension in terms of Witten and Marsden differentials.
The aim of this proposal is the study of single-particle states of $^{81}$Zn via the $^{80}$Zn(d,p) reaction in inverse kinematics. $^{81}$Zn will be produced by means of a laser-ionized, 5.5 MeV/u HIE-Isolde $^{80}$Zn beam impinging on a deuterated-polyethylene target. The protons and $\\gamma$-rays emitted in the reaction will be studied using the Miniball + T-REX setup. This experiment will constitute the first spectroscopic study of $^{81}$Zn, which is critically important to determine the energy and ordering of neutron single-particle orbits above the N=50 gap and the properties of $^{78}$Ni.
On Integrable Roots in Split Lie Triple Systems
Institute of Scientific and Technical Information of China (English)
A.J.CALDER(O)N MART(I)N
2009-01-01
We focus on the notion of an integrable root in the framework of split Lie triple systems T with a coherent 0-root space. As a main result, it is shown that if T has all its nonzero roots integrable, then its standard embedding is a split Lie algebra having all its nonzero roots integrable. As a consequence, a local finiteness theorem for split Lie triple systems, saying that whenever all nonzero roots of T are integrable then T is locally finite, is stated. Finally, a classification theorem for split simple Lie triple systems having all its nonzero roots integrable is given.
Historical Techniques of Lie Detection
Directory of Open Access Journals (Sweden)
Martina Vicianova
2015-08-01
Full Text Available Since time immemorial, lying has been a part of everyday life. For this reason, it has become a subject of interest in several disciplines, including psychology. The purpose of this article is to provide a general overview of the literature and thinking to date about the evolution of lie detection techniques. The first part explores ancient methods recorded circa 1000 B.C. (e.g., God’s judgment in Europe. The second part describes technical methods based on sciences such as phrenology, polygraph and graphology. This is followed by an outline of more modern-day approaches such as FACS (Facial Action Coding System, functional MRI, and Brain Fingerprinting. Finally, after the familiarization with the historical development of techniques for lie detection, we discuss the scope for new initiatives not only in the area of designing new methods, but also for the research into lie detection itself, such as its motives and regulatory issues related to deception.
Doublet-singlet model and unitarity
Cynolter, G.; Kovács, J.; Lendvai, E.
2016-12-01
We study the renormalizable singlet-doublet fermionic extension of the Standard Model (SM). In this model, the new vector-like fermions couple to the gauge bosons and to the Higgs via new Yukawa couplings that allow for nontrivial mixing in the new sector, providing a stable, neutral dark matter candidate. Approximate analytic formulae are given for the mass spectrum around the blind spots, where the dark matter candidate coupling to h or Z vanishes. We calculate the two particle scattering amplitudes in the model, impose the perturbative unitarity constraints and establish bounds on the Yukawa couplings.
Doublet-singlet model and unitarity
Cynolter, G; Lendvai, E
2016-01-01
We study the renormalizable singlet-doublet fermionic extension of the Standard Model. In this model, the new vector-like fermions couple to the gauge bosons and to the Higgs via new Yukawa couplings, that allow for nontrivial mixing in the new sector, providing a stable, neutral dark matter candidate. Approximate analytic formulae are given for the mass spectrum around the blind spots, where the dark matter candidate coupling to $h$ or $Z$ vanishes. We calculate the two particle scattering amplitudes in the model, impose the perturbative unitarity constraints and establish bounds on the Yukawa couplings.
Singlet deflected anomaly/gauge mediation
Energy Technology Data Exchange (ETDEWEB)
Blas, J. de, E-mail: jdeblasm@nd.edu [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Delgado, A., E-mail: antonio.delgado@nd.edu [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States)
2012-02-28
We study an extension of the standard anomaly/gauge mediation scenario where the messenger fields have direct interactions with an extra gauge singlet. This realizes a phenomenologically viable NMSSM-like scenario free of the {mu}-b{sub {mu}} problem. Current cosmological constraints imply a small size for the anomaly-mediation contributions, unless some source of R-parity violation is permitted. In the latter case the allowed regions in the parameter space can be substantially larger than in the corresponding gauge-mediation scenario.
Singlet-Triplet Transitions of a P(o)schl-Teller Quantum Dot
Institute of Scientific and Technical Information of China (English)
XIE Wen-Fang
2006-01-01
We study the energy spectra of a two-dimensional two-electron quantum dot (QD) with P(o)schl-Teller confining potential under the influence of perpendicular homogeneous magnetic field. Calculations are made by using the method of numerical diagonalization of Hamiltonian matrix within the effective-mass approximation. A ground-state behavior (spin singlet-triplet transitions) as a function of the strength of a magnetic field is found. We find that the dot radius R of a P(o)schl-Teller potential is important for the ground-state transition and the feature of ground-state for a P(o)schl-Teller QD and a parabolic QD is similar when R is larger. The larger the well depth, the higher the magnetic field for the singlet-triplet transition of the ground-state of two interacting electrons in a P(o)schl-Teller QD.
Structure of Solvable Quadratic Lie Algebras
Institute of Scientific and Technical Information of China (English)
ZHU Lin-sheng
2005-01-01
@@ Killing form plays a key role in the theory of semisimple Lie algebras. It is natural to extend the study to Lie algebras with a nondegenerate symmetric invariant bilinear form. Such a Lie algebra is generally called a quadratic Lie algebra which occur naturally in physics[10,12,13]. Besides semisimple Lie algebras, interesting quadratic Lie algebras include the Kac-Moody algebras and the Extended Affine Lie algebras.
Flavour singlets in gauge theory as Permutations
Kimura, Yusuke; Suzuki, Ryo
2016-01-01
Gauge-invariant operators can be specified by equivalence classes of permutations. We develop this idea concretely for the singlets of the flavour group $SO(N_f)$ in $U(N_c)$ gauge theory by using Gelfand pairs and Schur-Weyl duality. The singlet operators, when specialised at $N_f =6$, belong to the scalar sector of ${\\cal N}=4$ SYM. A simple formula is given for the two-point functions in the free field limit of $g_{YM}^2 =0$. The free two-point functions are shown to be equal to the partition function on a 2-complex with boundaries and a defect, in a topological field theory of permutations. The permutation equivalence classes are Fourier transformed to a representation basis which is orthogonal for the two-point functions at finite $N_c , N_f$. Counting formulae for the gauge-invariant operators are described. The one-loop mixing matrix is derived as a linear operator on the permutation equivalence classes.
Energy Technology Data Exchange (ETDEWEB)
Kasemann, Daniel
2012-02-27
densities. The triplet emitter system exhibits a slow rise of the EL after turn-on which prevents the usage of shorter pulses to enable higher current densities. The singlet emitter system, in contrast, exhibits a fast turn-on and reaches the maximum emission intensity within less than 20 ns. By several additional experiments including streak camera measurements and pump-probe experiments, the strong EL overshoot observed in the first few ns is successfully attributed to a reduced emission intensity in the steady state due to singlet-triplet annihilation. Hence, the separation of singlet emission and singlet-triplet quenching in time domain is demonstrated. At 550 A/cm{sup 2} and 10 ns pulse rise time, a peak luminance of 1.5.10{sup 6} cd/m{sup 2} is recorded. Finally, the experimental results are validated by modeling the singlet and triplet population dynamics in the emission layer of the fluorescent system to explain the time-resolved emission characteristics. Using a set of rate equations for the polaron density and the singlet and triplet exciton densities, the overshoot in singlet exciton density at the device turn-on is attributed to the separation of singlet emission and triplet quenching in time domain. Furthermore, by fitting the experimental data, the triplet-triplet annihilation rate in the host guest system is shown to become exciton density dependent at sufficiently high excitation density.
Singlet Exciton Lifetimes in Conjugated Polymer Films for Organic Solar Cells
Dimitrov, Stoichko
2016-01-13
The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact on the photocurrent generation by organic solar cell devices. However, very little is known about the material properties controlling the lifetimes of singlet excitons, with most of our knowledge originating from studies of small organic molecules. Herein, we provide a brief summary of the nature of the excited states in conjugated polymer films and then present an analysis of the singlet exciton lifetimes of 16 semiconducting polymers. The exciton lifetimes of seven of the studied polymers were measured using ultrafast transient absorption spectroscopy and compared to the lifetimes of seven of the most common photoactive polymers found in the literature. A plot of the logarithm of the rate of exciton decay vs. the polymer optical bandgap reveals a medium correlation between lifetime and bandgap, thus suggesting that the Energy Gap Law may be valid for these systems. This therefore suggests that small bandgap polymers can suffer from short exciton lifetimes, which may limit their performance in organic solar cell devices. In addition, the impact of film crystallinity on the exciton lifetime was assessed for a small bandgap diketopyrrolopyrrole co-polymer. It is observed that the increase of polymer film crystallinity leads to reduction in exciton lifetime and optical bandgap again in agreement with the Energy Gap Law.
Voltage-sensitive styryl dyes as singlet oxygen targets on the surface of bilayer lipid membrane.
Sokolov, V S; Gavrilchik, A N; Kulagina, A O; Meshkov, I N; Pohl, P; Gorbunova, Yu G
2016-08-01
Photosensitizers are widely used as photodynamic therapeutic agents killing cancer cells by photooxidation of their components. Development of new effective photosensitive molecules requires profound knowledge of possible targets for reactive oxygen species, especially for its singlet form. Here we studied photooxidation of voltage-sensitive styryl dyes (di-4-ANEPPS, di-8-ANEPPS, RH-421 and RH-237) by singlet oxygen on the surface of bilayer lipid membranes commonly used as cell membrane models. Oxidation was induced by irradiation of a photosensitizer (aluminum phthalocyanine tetrasulfonate) and monitored by the change of dipole potential on the surface of the membrane. We studied the drop of the dipole potential both in the case when the dye molecules were adsorbed on the same side of the lipid bilayer as the photosensitizer (cis-configuration) and in the case when they were adsorbed on the opposite side (trans-configuration). Based on a simple model, we determined the rate of oxidation of the dyes from the kinetics of change of the potential during and after irradiation. This rate is proportional to steady-state concentration of singlet oxygen in the membrane under irradiation. Comparison of the oxidation rates of various dyes reveals that compounds of ANEPPS series are more sensitive to singlet oxygen than RH type dyes, indicating that naphthalene group is primarily responsible for their oxidation.
Singlet Exciton Lifetimes in Conjugated Polymer Films for Organic Solar Cells
Directory of Open Access Journals (Sweden)
Stoichko D. Dimitrov
2016-01-01
Full Text Available The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact on the photocurrent generation by organic solar cell devices. However, very little is known about the material properties controlling the lifetimes of singlet excitons, with most of our knowledge originating from studies of small organic molecules. Herein, we provide a brief summary of the nature of the excited states in conjugated polymer films and then present an analysis of the singlet exciton lifetimes of 16 semiconducting polymers. The exciton lifetimes of seven of the studied polymers were measured using ultrafast transient absorption spectroscopy and compared to the lifetimes of seven of the most common photoactive polymers found in the literature. A plot of the logarithm of the rate of exciton decay vs. the polymer optical bandgap reveals a medium correlation between lifetime and bandgap, thus suggesting that the Energy Gap Law may be valid for these systems. This therefore suggests that small bandgap polymers can suffer from short exciton lifetimes, which may limit their performance in organic solar cell devices. In addition, the impact of film crystallinity on the exciton lifetime was assessed for a small bandgap diketopyrrolopyrrole co-polymer. It is observed that the increase of polymer film crystallinity leads to reduction in exciton lifetime and optical bandgap again in agreement with the Energy Gap Law.
Lie bialgebras of generalized Witt type
Institute of Scientific and Technical Information of China (English)
SONG; Guang'ai; SU; Yucai
2006-01-01
In this paper, all Lie bialgebra structures on the Lie algebras of generalized Witt type are considered. It is proved that, for any Lie algebra W of generalized Witt type, all Lie bialgebras on W are the coboundary triangular Lie bialgebras. As a by-product, it is also proved that the first cohomology group H1(W, W (x) W) is trivial.
An evaluation on Real Semisimple Lie Algebras
Institute of Scientific and Technical Information of China (English)
无
2000-01-01
@@ The theory of Lie groups and Lie algebras stem from that of continuous groups founded by Sophus Lie at the end of 19th century. From the beginning, the theory of Lie groups and Lie algebras has displayed great value in both theoretical researches and applications.
Cohomology of Heisenberg Lie superalgebras
Bai, Wei; Liu, Wende
2017-02-01
Suppose the ground field to be algebraically closed and of characteristic different from 2 and 3. All Heisenberg Lie superalgebras consist of two super-versions of the Heisenberg Lie algebras, 𝔥2m,n and 𝔟𝔞n with m a non-negative integer and n a positive integer. The space of a "classical" Heisenberg Lie superalgebra 𝔥2m,n is the direct sum of a superspace with a non-degenerate anti-supersymmetric even bilinear form and a one-dimensional space of values of this form constituting the even center. The other super-analog of the Heisenberg Lie algebra, 𝔟𝔞n, is constructed by means of a non-degenerate anti-supersymmetric odd bilinear form with values in the one-dimensional odd center. In this paper, we study the cohomology of 𝔥2m,n and 𝔟𝔞n with coefficients in the trivial module by using the Hochschild-Serre spectral sequences relative to a suitable ideal. In the characteristic zero case, for any Heisenberg Lie superalgebra, we determine completely the Betti numbers and associative superalgebra structures for their cohomology. In the characteristic p > 3 case, we determine the associative superalgebra structure for the divided power cohomology of 𝔟𝔞n and we also make an attempt to determine the divided power cohomology of 𝔥2m,n by computing it in a low-dimensional case.
Langs, R
In this paper an attempt is made to conceptualize a basic dimension of various psychotherapeutic treatment modalities, especially psychoanalysis and psychoanalytically oriented psychotherapy. The central variable under consideration is the extent to which each endeavors to approach the truth within both patient and therapist as it exists dynamically in terms of their spiraling unconscious communicative interaction. That treatment modality which takes into account every possible dimension of such truths is termed truth therapy. Treatment modalities that make no attempt to arrive at these truths or that deliberately or inadvertently falsify their nature are termed lie or barrier therapies. Extensive consideration is given to truth therapy and the truth system on which it is based. The basis for the need for lie therapies is explored, and lie systems, which may arise from either patient or therapist, or both, are identified. A classification of common types of lie patients and lie therapists (and their main techniques) is offered. The implications of this delineation for our understanding of the dynamic therapies are discussed, and a number of new clinical issues arising from this perspective are addressed.
Transient photocurrent in molecular junctions: singlet switching on and triplet blocking.
Petrov, E G; Leonov, V O; Snitsarev, V
2013-05-14
The kinetic approach adapted to describe charge transmission in molecular junctions, is used for the analysis of the photocurrent under conditions of moderate light intensity of the photochromic molecule. In the framework of the HOMO-LUMO model for the single electron molecular states, the analytic expressions describing the temporary behavior of the transient and steady state sequential (hopping) as well as direct (tunnel) current components have been derived. The conditions at which the current components achieve their maximal values are indicated. It is shown that if the rates of charge transmission in the unbiased molecular diode are much lower than the intramolecular singlet-singlet excitation/de-excitation rate, and the threefold degenerated triplet excited state of the molecule behaves like a trap blocking the charge transmission, a possibility of a large peak-like transient switch-on photocurrent arises.
DEFF Research Database (Denmark)
Andersen, Torkild; Maack Bisgård, K.; Hansen, P.Gregers
1961-01-01
The decay of 1.6 × 105y U233 has been studied by means of a six gap beta-ray spectrometer, a xenon filled proportional counter and scintillation spectrometers. Internal conversion electrons having energies below 100 keV were measured. The mixing ratios for the 42 keV and the 55 keV transitions ag...
Finite dimensional quadratic Lie superalgebras
Jarvis, Peter; Yates, Luke
2010-01-01
We consider a special class of Z_2-graded, polynomial algebras of degree 2, which we call quadratic Lie superalgebras. Starting from the formal definition, we discuss the generalised Jacobi relations in the context of the Koszul property, and give a proof of the PBW basis theorem. We give several concrete examples of quadratic Lie superalgebras for low dimensional cases, and discuss aspects of their structure constants for the `type I' class. Based on the factorisation of the enveloping algebra, we derive the Kac module construction for typical and atypical modules, and a related direct construction of irreducible modules due to Gould. We investigate the method for one specific case, the quadratic generalisation gl_2(n/1) of the Lie superalgebra sl(n/1). We formulate the general atypicality conditions at level 1, and present an analysis of zero-and one-step atypical modules for a certain family of Kac modules.
Indian Academy of Sciences (India)
Antonio J Calderón Martín
2009-04-01
We begin the study of arbitrary split Lie triple systems by focussing on those with a coherent 0-root space. We show that any such triple systems with a symmetric root system is of the form $T=\\mathcal{U}+\\sum_j I_j$ with $\\mathcal{U}$ a subspace of the 0-root space $T_0$ and any $I_j$ a well described ideal of , satisfying $[I_j,T,I_k]=0$ if $j≠ k$. Under certain conditions, it is shown that is the direct sum of the family of its minimal ideals, each one being a simple split Lie triple system, and the simplicity of is characterized. The key tool in this job is the notion of connection of roots in the framework of split Lie triple systems.
Loop Virasoro Lie conformal algebra
Energy Technology Data Exchange (ETDEWEB)
Wu, Henan, E-mail: wuhenanby@163.com; Chen, Qiufan; Yue, Xiaoqing [Department of Mathematics, Tongji University, Shanghai 200092 (China)
2014-01-15
The Lie conformal algebra of loop Virasoro algebra, denoted by CW, is introduced in this paper. Explicitly, CW is a Lie conformal algebra with C[∂]-basis (L{sub i} | i∈Z) and λ-brackets [L{sub i} {sub λ} L{sub j}] = (−∂−2λ)L{sub i+j}. Then conformal derivations of CW are determined. Finally, rank one conformal modules and Z-graded free intermediate series modules over CW are classified.
Topological spin-singlet superconductors with underlying sublattice structure
Dutreix, C.
2017-07-01
Majorana boundary quasiparticles may naturally emerge in a spin-singlet superconductor with Rashba spin-orbit interactions when a Zeeman magnetic field breaks time-reversal symmetry. Their existence and robustness against adiabatic changes is deeply related, via a bulk-edge correspondence, to topological properties of the band structure. The present paper shows that the spin-orbit may be responsible for topological transitions when the superconducting system has an underlying sublattice structure, as it appears in a dimerized Peierls chain, graphene, and phosphorene. These systems, which belong to the Bogoliubov-de Gennes class D, are found to have an extra symmetry that plays the role of the parity. It enables the characterization of the topology of the particle-hole symmetric band structure in terms of band inversions. The topological phase diagrams this leads to are then obtained analytically and exactly. They reveal that, because of the underlying sublattice structure, the existence of topological superconducting phases requires a minimum doping fixed by the strength of the Rashba spin orbit. Majorana boundary quasiparticles are finally predicted to emerge when the Fermi level lies in the vicinity of the bottom (top) of the conduction (valence) band in semiconductors such as the dimerized Peierls chain and phosphorene. In a two-dimensional topological superconductor based on (stretched) graphene, which is semimetallic, Majorana quasiparticles cannot emerge at zero and low doping, that is, when the Fermi level is close to the Dirac points. Nevertheless, they are likely to appear in the vicinity of the van Hove singularities.
Isomorphism of Intransitive Linear Lie Equations
Directory of Open Access Journals (Sweden)
Jose Miguel Martins Veloso
2009-11-01
Full Text Available We show that formal isomorphism of intransitive linear Lie equations along transversal to the orbits can be extended to neighborhoods of these transversal. In analytic cases, the word formal is dropped from theorems. Also, we associate an intransitive Lie algebra with each intransitive linear Lie equation, and from the intransitive Lie algebra we recover the linear Lie equation, unless of formal isomorphism. The intransitive Lie algebra gives the structure functions introduced by É. Cartan.
Shu, Yu-Rong; Yao, Dao-Xin; Ke, Chih-Wei; Lin, Yu-Cheng; Sandvik, Anders W.
2016-11-01
We use a strong-disorder renormalization group (SDRG) method and ground-state quantum Monte Carlo (QMC) simulations to study S =1 /2 spin chains with random couplings, calculating disorder-averaged spin and dimer correlations. The QMC simulations demonstrate logarithmic corrections to the power-law decaying correlations obtained with the SDRG scheme. The same asymptotic forms apply both for systems with standard Heisenberg exchange and for certain multispin couplings leading to spontaneous dimerization in the clean system. We show that the logarithmic corrections arise in the valence-bond (singlet pair) basis from a contribution that cannot be generated by the SDRG scheme. In the model with multispin couplings, where the clean system dimerizes spontaneously, random singlets form between spinons localized at domain walls in the presence of disorder. This amorphous valence-bond solid is asymptotically a random-singlet state and only differs from the random-exchange Heisenberg chain in its short-distance properties.
Singlet Scalar Resonances and the Diphoton Excess
McDermott, Samuel D; Ramani, Harikrishnan
2015-01-01
ATLAS and CMS recently released the first results of searches for diphoton resonances in 13 TeV data, revealing a modest excess at an invariant mass of approximately 750 GeV. We find that it is generically possible that a singlet scalar resonance is the origin of the excess while avoiding all other constraints. We highlight some of the implications of this model and how compatible it is with certain features of the experimental results. In particular, we find that the very large total width of the excess is difficult to explain with loop-level decays alone, pointing to other interesting bounds and signals if this feature of the data persists. Finally we comment on the robust Z-gamma signature that will always accompany the model we investigate.
Vdovin, Alexander; Sepioł, Jerzy; Urbańska, Natalia; Pietraszkiewicz, Marek; Mordziński, Andrzej; Waluk, Jacek
2006-03-01
Laser-induced fluorescence and dispersed fluorescence spectra measured in supersonic jets for 9,10,19,20-tetra-n-methylporphycene and 9,10,19,20-tetra-n-propylporphycene reveal, for both compounds, the presence of two different species which are assigned to trans and cis tautomeric forms. Doublet splitting of lines is observed, disappearing upon deuteration of the inner nitrogen atoms. This finding is interpreted as an indication of double hydrogen tunneling. The values of tunneling splitting are obtained for both ground and lowest singlet excited states. The splitting is similar for cis and trans forms, and the barrier for tautomerization is larger in the excited state. Due to the coupling of hydrogen motion with rotation of alkyl substituents, tautomerization occurs in an asymmetric double minimum potential, with the ordering of energy minima reversed upon excitation. The second singlet excited state is found to lie very close to S(1), thus facilitating an efficient radiationless depopulation.
Cartan Connections and Lie Algebroids
Directory of Open Access Journals (Sweden)
Michael Crampin
2009-06-01
Full Text Available This paper is a study of the relationship between two constructions associated with Cartan geometries, both of which involve Lie algebroids: the Cartan algebroid, due to [Blaom A.D., Trans. Amer. Math. Soc. 358 (2006, 3651–3671], and tractor calculus [Cap A., Gover A.R., Trans. Amer. Math. Soc. 354 (2001, 1511–1548].
Cartan Connections and Lie Algebroids
Crampin, Michael
2009-01-01
This paper is a study of the relationship between two constructions associated with Cartan geometries, both of which involve Lie algebroids: the Cartan algebroid, due to [Blaom A.D., Trans. Amer. Math. Soc. 358 (2006), 3651-3671], and tractor calculus [Cap A., Gover A.R., Trans. Amer. Math. Soc. 354 (2001), 1511-1548].
String Topology for Lie Groups
DEFF Research Database (Denmark)
A. Hepworth, Richard
2010-01-01
In 1999 Chas and Sullivan showed that the homology of the free loop space of an oriented manifold admits the structure of a Batalin-Vilkovisky algebra. In this paper we give a direct description of this Batalin-Vilkovisky algebra in the case that the manifold is a compact Lie group G. Our answer ...
Stasheuski, Alexander S; Galievsky, Victor A; Stupak, Alexander P; Dzhagarov, Boris M; Choi, Mi Jin; Chung, Bong Hyun; Jeong, Jin Young
2014-01-01
As various fullerene derivatives have been developed, it is necessary to explore their photophysical properties for potential use in photoelectronics and medicine. Here, we address the photophysical properties of newly synthesized water-soluble fullerene-based nanoparticles and polyhydroxylated fullerene as a representative water-soluble fullerene derivative. They show broad emission band arising from a wide-range of excitation energies. It is attributed to the optical transitions from disorder-induced states, which decay in the nanosecond time range. We determine the kinetic properties of the singlet oxygen (1O2) luminescence generated by the fullerene nanoparticles and polyhydroxylated fullerene to consider the potential as photodynamic agents. Triplet state decay of the nanoparticles was longer than 1O2 lifetime in water. Singlet oxygen quantum yield of a series of the fullerene nanoparticles is comparably higher ranging from 0.15 to 0.2 than that of polyhydroxylated fullerene, which is about 0.06. PMID:24893622
Singlet-triplet annihilation limits exciton yield in poly(3-hexylthiophene)
Steiner, Florian; Lupton, John M
2014-01-01
Control of chain length and morphology in combination with single-molecule spectroscopy techniques provide a comprehensive photophysical picture of excited-state losses in the prototypical conjugated polymer poly(3-hexylthiophene) (P3HT). A universal self-quenching mechanism is revealed, 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 bulk-like (folded) state. Triplet excitons fundamentally limit the fluorescence of organic photovoltaic materials, which impacts on the conversion of singlet excitons to separated charge carriers, decreasing the efficiency of energy harvesting at high excitation densities. Interexcitonic interactions are so effective that a single P3HT chain of >100 kDa weight behaves like a two-level system, exhibiting perfect photon-antibunching.
Topological order, symmetry, and Hall response of two-dimensional spin-singlet superconductors
Moroz, Sergej; Gurarie, Victor; Radzihovsky, Leo
2016-01-01
Fully gapped two-dimensional superconductors coupled to dynamical electromagnetism are known to exhibit topological order. In this work, we develop a unified low-energy description for spin-singlet paired states by deriving topological Chern-Simons field theories for $s$-wave, $d+id$, and chiral higher even-wave superconductors. These theories capture the quantum statistics and fusion rules of low-energy excitations and incorporate global continuous symmetries - specifically, spin rotation and conservation of magnetic flux - present in all singlet superconductors. We compute the Hall response for these symmetries and investigate the physics at the edge. In particular, the weakly-coupled phase of a chiral state paired in the even $k^{\\text{th}}$ partial wave has a spin Hall coefficient $\
Quantum Computing via Singlet-Triplet Spin Qubits in Nanowire Double Quantum Dots
Institute of Scientific and Technical Information of China (English)
XUE Peng
2011-01-01
We propose a new structure for quantum computing via spin qubits with high fidelity.Each spin qubit corresponds to two electrons in a nanowire double quantum dot,with the singlet and one of the triplets as the logical qubit states.The entangling gate is effected by virtual charge dipole transitions.We include noise to show the feasibility of this scheme under current experimental conditions.
The electroweak phase transition in models with gauge singlets
Energy Technology Data Exchange (ETDEWEB)
Ahriche, A.
2007-04-18
A strong first order phase transition is needed for generating the baryon asymmetry; and also to save it during the electroweak phase transition (EWPT). However this condition is not fulfilled within the Standard Model (SM), but in its extensions. It is widely believed that the existence of singlet scalars in some Standard Model extensions can easily make the EWPT strongly first order. In this work, we will examine the strength of the EWPT in the simplest extension of the SM with a real gauge singlet using the sphaleron energy at the critical temperature. We find that the phase transition is stronger by adding a singlet; and also that the criterion for a strong phase transition {omega}(T{sub c})/T{sub c} >or similar 1, where {omega} = (v{sup 2} + (x - x{sub 0}){sup 2}){sup (}1)/(2) and x(x{sub 0}) is the singlet vacuum expectation value in the broken (symmetric) phase, is not valid for models containing singlets, even though often used in the literature. The usual condition v{sub c}/T{sub c} >or similar 1 is more meaningful, and it is satisfied for the major part of the parameter space for physically allowed Higgs masses. Then it is convenient to study the EWPT in models with singlets that couple only to the Higgs doublets, by replacing the singlets by their vevs. (orig.)
Spherical functions on affine Lie groups
Etingof, P; Kirillov, A A; Pavel Etingof; Igor Frenkel; Alexander Kirillov Jr
1994-01-01
We show that the space of holomorphic functions of a fixed degree on an affine Lie group which take values in a finite-dimensional representation of this group and are equivariant with respect to (twisted) conjugacy coin- cides with the space of conformal blocks of the Wess-Zumino-Witten conformal field theory on an elliptic curve with punctures, or, equivalently,with the space of states of the Chern-Simons topological field theory in genus 1. This provides a group-theoretic realization of the Segal modular functor for elliptic curves. We also show that the the radial part of the second order Laplace operator on an affine Lie group acting in the space of equivariant functions coincides with the operator defining the Knizhnik-Zamolodchikov connection on conformal blocks on elliptic curves, and its eigenfunctions coincide with the correlation functions of conformal blocks. At the critical value of the degree (minus the dual Coxeter number of the underlying simple Lie algebra) there exist higher order Laplace op...
Topological order, symmetry, and Hall response of two-dimensional spin-singlet superconductors
Moroz, Sergej; Prem, Abhinav; Gurarie, Victor; Radzihovsky, Leo
2017-01-01
Fully gapped two-dimensional superconductors coupled to dynamical electromagnetism are known to exhibit topological order. In this work, we develop a unified low-energy description for spin-singlet paired states by deriving topological Chern-Simons field theories for s -wave, d +i d , and chiral higher even-wave superconductors. These theories capture the quantum statistics and fusion rules of Bogoliubov quasiparticles and vortices and incorporate global continuous symmetries—specifically, spin rotation and conservation of magnetic flux—present in all singlet superconductors. For all such systems, we compute the Hall response for these symmetries and investigate the physics at the edge. In particular, the weakly coupled phase of a chiral d +i d chiral state has a spin Hall coefficient νs=2 and a vanishing Hall response for the magnetic flux symmetry. We argue that the latter is a generic result for two-dimensional superconductors with gapped photons, thereby demonstrating the absence of a spontaneous magnetic field in the ground state of chiral superconductors. It is also shown that the Chern-Simons theories of chiral spin-singlet superconductors derived here fall into Kitaev's 16-fold classification of topological superconductors.
Quantum dynamics study of singlet-triplet transitions in s-trans-1,3-butadiene
Nikoobakht, Behnam; Köppel, Horst
2016-05-01
The intersystem crossing dynamics of s-trans-1,3-butadiene in its lowest singlet and triplet states is studied theoretically, employing a fully quantal approach for the first time. The electronic states 21Ag, 11Bu, 13Bu and 13Ag, which interact vibronically and via the spin-orbit coupling are treated in the calculation, thus covering the lowest spin-forbidden electronic transitions. Up to five nuclear degrees of freedom, including out-of-plane dihedral angles are included in our investigation. The calculation of potential energy surfaces relies on the CASPT2 method, and the evaluation of spin-orbit coupling matrix elements using the full two-electron Breit-Pauli Hamiltonian is performed by utilizing the MRCI wavefunction. The latter dependence on the nuclear coordinates is included for the first time. An electronic population transfer on the sub-picosecond time scale due to intersystem crossing is obtained, a mechanism that can contribute to the singlet-triplet transitions in the electron energy loss spectrum of s-trans-1, 3-butadiene. It is found that the dependence of the spin-orbit coupling on the out-of-plane coordinates plays a dominant role in these singlet-triplet transitions. The amount of population transfer to the 13Ag and 13Bu states is roughly of the same order of magnitude.
Sun, Zhe
2013-12-04
Clar\\'s aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar\\'s aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.
Symmetry via Lie algebra cohomology
Eastwood, Michael
2010-01-01
The Killing operator on a Riemannian manifold is a linear differential operator on vector fields whose kernel provides the infinitesimal Riemannian symmetries. The Killing operator is best understood in terms of its prolongation, which entails some simple tensor identities. These simple identities can be viewed as arising from the identification of certain Lie algebra cohomologies. The point is that this case provides a model for more complicated operators similarly concerned with symmetry.
Almost-Riemannian Geometry on Lie Groups
Ayala, Victor; Jouan, Philippe
2015-01-01
A simple Almost-Riemmanian Structure on a Lie group G is defined by a linear vector field and dim(G)-1 left-invariant ones. We state results about the singular locus, the abnormal extremals and the desingularization of such ARS's, and these results are illustrated by examples on the 2D affine and the Heisenberg groups.These ARS's are extended in two ways to homogeneous spaces, and a necessary and sufficient condition for an ARS on a manifold to be equivalent to a general ARS on a homogeneous ...
Corbett, Tyler; Gonzalez-Garcia, M C
2015-01-01
We explore the use of the Inverse Amplitude Method for unitarization of scattering amplitudes to derive the existence and properties of possible new heavy states associated with perturbative extensions of the electroweak breaking sector of the Standard Model starting from the low energy effective theory. We use a toy effective theory generated by integrating out a heavy singlet scalar and compare the pole mass and width of the unitarized amplitudes with those of the original model. Our results show that the Inverse Amplitude Method reproduces correctly the singlet mass up to factors of O(1-3), but its width is overestimated.
Can Lies Be Detected Unconsciously?
Directory of Open Access Journals (Sweden)
David eShanks
2015-08-01
Full Text Available People are typically poor at telling apart truthful and deceptive statements. Based on the Unconscious Thought Theory, it has been suggested that poor lie detection arises from the intrinsic limitations of conscious thinking and can be improved by facilitating the contribution of unconscious thought. In support of this hypothesis, Reinhard, Greifeneder, and Scharmach (2013 observed improved lie detection among participants engaging in unconscious thought. The present study aimed to replicate this unconscious thought advantage using a similar experimental procedure but with an important improvement in a key control condition. Specifically, participants judged the truthfulness of 8 video recordings in three thinking modes: immediately after watching them or after a period of unconscious or conscious deliberation. Results from two experiments (combined N = 226 failed to reveal a significant difference in lie detection accuracy between the thinking modes, even after efforts were made to facilitate the occurrence of an unconscious thought advantage in Experiment 2. The results imply that the unconscious thought advantage in deception detection is not a robust phenomenon.
q-deformed Lie algebras and fractional calculus
Herrmann, Richard
2007-01-01
Fractional calculus and q-deformed Lie algebras are closely related. Both concepts expand the scope of standard Lie algebras to describe generalized symmetries. For the fractional harmonic oscillator, the corresponding q-number is derived. It is shown, that the resulting energy spectrum is an appropriate tool e.g. to describe the ground state spectra of even-even nuclei. In addition, the equivalence of rotational and vibrational spectra for fractional q-deformed Lie algebras is shown and the $B_\\alpha(E2)$ values for the fractional q-deformed symmetric rotor are calculated.
DEFF Research Database (Denmark)
Helbig, M.; Ruseckas, A.; Grage, M.M.-L.
1999-01-01
Photoexcitation dynamics of terthiophene (3T) molecules incorporated in an organic-inorganic matrix containing titanium in the network are investigated by polarized transient absorption with femtosecond time resolution. We observed the decay of excited-state absorption of neutral 3T and simultane......Photoexcitation dynamics of terthiophene (3T) molecules incorporated in an organic-inorganic matrix containing titanium in the network are investigated by polarized transient absorption with femtosecond time resolution. We observed the decay of excited-state absorption of neutral 3T...... is an attractive feature for application in photovoltaic devices. (C) 1999 Elsevier Science B.V. All rights reserved....
The nature of singlet excitons in oligoacene molecular crystals
Yamagata, H.
2011-01-01
A theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32cm-1, far smaller than the measured value of 631cm-1 and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601cm-1 and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport. © 2011 American Institute of Physics.
Particle-like structure of Lie algebras
Vinogradov, A. M.
2017-07-01
If a Lie algebra structure 𝔤 on a vector space is the sum of a family of mutually compatible Lie algebra structures 𝔤i's, we say that 𝔤 is simply assembled from the 𝔤i's. Repeating this procedure with a number of Lie algebras, themselves simply assembled from the 𝔤i's, one obtains a Lie algebra assembled in two steps from 𝔤i's, and so on. We describe the process of modular disassembling of a Lie algebra into a unimodular and a non-unimodular part. We then study two inverse questions: which Lie algebras can be assembled from a given family of Lie algebras, and from which Lie algebras can a given Lie algebra be assembled. We develop some basic assembling and disassembling techniques that constitute the elements of a new approach to the general theory of Lie algebras. The main result of our theory is that any finite-dimensional Lie algebra over an algebraically closed field of characteristic zero or over R can be assembled in a finite number of steps from two elementary constituents, which we call dyons and triadons. Up to an abelian summand, a dyon is a Lie algebra structure isomorphic to the non-abelian 2-dimensional Lie algebra, while a triadon is isomorphic to the 3-dimensional Heisenberg Lie algebra. As an example, we describe constructions of classical Lie algebras from triadons.
Garza, Alejandro J; Scuseria, Gustavo E
2015-01-01
Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The $f^0$ actinyl series (UO$_2^{2+}$, NpO$_2^{2+}$, PuO$_2^{2+}$), the isoelectronic NUN, and Thorium (ThO, ThO$^{2+}$) and Nobelium (NoO, NoO$_2$) oxides are studied.
Directory of Open Access Journals (Sweden)
Ashraf Khademzadeh
2014-01-01
Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.
Singlet exciton fission in nanostructured organic solar cells.
Jadhav, Priya J; Mohanty, Aseema; Sussman, Jason; Lee, Jiye; Baldo, Marc A
2011-04-13
Singlet exciton fission is an efficient multiexciton generation process in organic molecules. But two concerns must be satisfied before it can be exploited in low-cost solution-processed organic solar cells. Fission must be combined with longer wavelength absorption in a structure that can potentially surpass the single junction limit, and its efficiency must be demonstrated in nanoscale domains within blended devices. Here, we report organic solar cells comprised of tetracene, copper phthalocyanine, and the buckyball C(60). Short wavelength light generates singlet excitons in tetracene. These are subsequently split into two triplet excitons and transported through the phthalocyanine. In addition, the phthalocyanine absorbs photons below the singlet exciton energy of tetracene. To test tetracene in nanostructured blends, we fabricate coevaporated bulk heterojunctions and multilayer heterojunctions of tetracene and C(60). We measure a singlet fission efficiency of (71 ± 18)%, demonstrating that exciton fission can efficiently compete with exciton dissociation on the nanoscale.
Singlet model interference effects with high scale UV physics
Dawson, S.; Lewis, I. M.
2017-01-01
One of the simplest extensions of the Standard Model (SM) is the addition of a scalar gauge singlet, S . If S is not forbidden by a symmetry from mixing with the Standard Model Higgs boson, the mixing will generate non-SM rates for Higgs production and decays. In general, there could also be unknown high energy physics that generates additional effective low energy interactions. We show that interference effects between the scalar resonance of the singlet model and the effective field theory (EFT) operators can have significant effects in the Higgs sector. We examine a non-Z2 symmetric scalar singlet model and demonstrate that a fit to the 125 GeV Higgs boson couplings and to limits on high mass resonances, S , exhibit an interesting structure and possible large cancellations of effects between the resonance contribution and the new EFT interactions, that invalidate conclusions based on the renormalizable singlet model alone.
Singlet Oxygen Generation Mediated By Silicon Nanocrystal Assemblies
2011-01-01
respect to conventional sources. Absorption maxima of dye photosensitizers used for singlet oxygen generation are between 630 to 700 nm. On the other hand...in aqueous solutions is its photodegradation due to photooxidation. This process drastically reduces photosensitizing ability of Si nanocrystals in a...above. Thus, the efficiency of photodegradation of organic molecules by singlet oxygen generated by PSi strongly depends on the nature of
[Decrease of singlet oxygen chemiluminescence by the presence of carnosine].
Svachko, A G; Formaziuk, V E; Sergienko, V I
1990-08-01
To test antiradical medicines effect the chemical production of singlet oxygen (NaClO + H2O2) was investigated. The quantity singlet oxygen chemiluminescence was decreased in the presence of Japanese Catalin and Chine Baineiting, antirheumatic Voltaren and less strong Finish Catachrome and Carnosine. American Quinax does not possess such an effect. One of the possible starting mechanisms causing different diseases (atherosclerosis, cataract etc.) is destruction of biomembranes by active forms of oxygen.
Directory of Open Access Journals (Sweden)
Kaneez Fatima
2016-02-01
Full Text Available Photodynamic therapy (PDT is one of the methods involved in cancer therapy exploiting singlet oxygen as a weapon to kill cancer cells. Singlet oxygen, a bizarre reactive oxygen species as it is not related to electron transfer to O2 but it is one of the most active intermediate involved in biochemical reactions as it directly reacts with all the major macromolecules like DNA, protein, lipids etc, various photosensitized oxidations and in the photodegradation of dyes and polymers. Recent studies about the usage of antioxidant along with the photo-sensitizer involved in photodynamic therapy have shown concentration- dependent dual behavior like usually it retards the efficacy of PDT but at a higher dose mostly, it actually enhances the damaging effect of PDT. The natural and synthetic antioxidants are being used in our day to day life in order to increase the shelf life of various food ingredients and processed foods. In this paper, we have compared natural and synthetic antioxidants along with the known singlet oxygen quencher (DABCO in order to understand the quenching potential of singlet oxygen (1O2 which is lowest electronically excited state of molecular oxygen. The singlet oxygen can be artificially generated through various methods such as sunlight, phosphate, ozonides, NaOCl and H2O2 etc. We have studied the mechanisms of the few antioxidant effects on the bleaching of RNO linked with the energy decay of 1O2 produced by the Mallet reaction (H2O2+HOCl and #8200; and #8594; and #8200;HCl+H2O+1O2. beta-Carotene, and #945;-Tocopherol, Ascorbic acid and Quercetin exhibited best dose-dependent singlet quenching ranging from 92.3 to 56.5 % at 100 and #956;M among others. Overall singlet oxygen is a major concern of light-related properties so we have analyzed the theoretical aspect of electronic UV/visible absorption spectra of the antioxidants studied through ZINDO CI semi-empirical Hamiltonian method. We have compared only the first singlet
Knicker, Heike
2016-04-01
"Nuclear magnetic resonance (NMR) does not lie". More than anything else, this statement of a former colleague and friend has shaped my relation to solid-state NMR spectroscopy. Indeed, if this technique leads to results which contradict the expectations, it is because i) some parts of the instrument are broken, ii) maladjustment of the acquisition parameters or iii) wrong preparation or confusion of samples. However, it may be even simpler, namely that the expectations were wrong. Of course, for researchers, the latter is the most interesting possibility since it forces to reassess accepted views and to search for new explanations. As my major analytical tool, NMR spectroscopy has confronted me with this challenge often enough to turn this issue into the main subject of my talk and to share with the audience how it formed my understanding of function and nature of soil organic matter (SOM). Already shortly after its introduction into soil science in the 1980's, the data obtained with solid-state 13C NMR spectroscopy opened the stage for ongoing discussions, since they showed that in humified SOM aromatic carbon is considerably less important than previously thought. This finding had major implications regarding the understanding of the origin of SOM and the mechanisms by which it is formed. Certainly, the discrepancy between the new results and previous paradigms contributed to mistrust in the reliability of solid-state NMR techniques. The respective discussion has survived up to our days, although already in the 1980's and 1990's fundamental studies could demonstrate that quantitative solid-state NMR data can be obtained if i) correct acquisition parameters are chosen, ii) the impact of paramagnetic compounds is reduced and iii) the presence of soot in soils can be excluded. On the other hand, this mistrust led to a detailed analysis of the impact of paramagnetics on the NMR behavior of C groups which then improved our understanding of the role of carbohydrates
Filiform Lie algebras of order 3
Navarro, R. M.
2014-04-01
The aim of this work is to generalize a very important type of Lie algebras and superalgebras, i.e., filiform Lie (super)algebras, into the theory of Lie algebras of order F. Thus, the concept of filiform Lie algebras of order F is obtained. In particular, for F = 3 it has been proved that by using infinitesimal deformations of the associated model elementary Lie algebra it can be obtained families of filiform elementary lie algebras of order 3, analogously as that occurs into the theory of Lie algebras [M. Vergne, "Cohomologie des algèbres de Lie nilpotentes. Application à l'étude de la variété des algèbres de Lie nilpotentes," Bull. Soc. Math. France 98, 81-116 (1970)]. Also we give the dimension, using an adaptation of the {sl}(2,{C})-module Method, and a basis of such infinitesimal deformations in some generic cases.
Transformation groups and Lie algebras
Ibragimov, Nail H
2013-01-01
This book is based on the extensive experience of teaching for mathematics, physics and engineering students in Russia, USA, South Africa and Sweden. The author provides students and teachers with an easy to follow textbook spanning a variety of topics. The methods of local Lie groups discussed in the book provide universal and effective method for solving nonlinear differential equations analytically. Introduction to approximate transformation groups also contained in the book helps to develop skills in constructing approximate solutions for differential equations with a small parameter.
One-Loop Radiative Correction to the Triple Higgs Coupling in the Higgs Singlet Model
He, Shi-Ping
2016-01-01
Though the 125 GeV Higgs boson is consistent with the standard model (SM) prediction until now, the triple coupling can deviate from the SM value in the physics beyond the SM (BSM). In this paper, the radiative correction to the triple Higgs coupling is calculated in the minimal extension of the SM by adding a real gauge singlet scalar. In this model there are two scalars $h$ and $H$ and both of them are mixed states of the doublet and singlet. Provided that the mixing angle is set to be zero, $h$ is the pure left-over of the doublet and its behavior is the same as that of the SM except the triple $h$ couping. In this SM limit case, the effect of the singlet $H$ will decouple from the fermions and gauge bosons, and firstly shown up in the triple $h$ coupling. Our numerical results show that the deviation is sizable. For $\\lambda_{\\Phi{S}}=1$ (see text for the parameter definition), the deviation $\\delta_{hhh}^{(1)}$ can be $40\\%$. For $\\lambda_{\\Phi{S}}=1.5$, the $\\delta_{hhh}^{(1)}$ can reach $140\\%$. The si...
Monitoring of singlet oxygen in the lower troposphere and processes of ozone depletion.
Iasenko, Egor; Chelibanov, Vladimir; Marugin, Alexander; Kozliner, Marat
2016-04-01
The processes of ozone depletion in the atmosphere are widely discussed now in a connection with the problem of a global climate changes. It is known fact that photolysis of ozone in the upper atmosphere is the source of metastable molecules of oxygen. But, metastable molecules of oxygen can be formed as a result of photo initiated heterogeneous oxidation of molecules adsorbed on the surface of natural aerosol particles. During the outdoor experiment, we observed a formation of Singlet oxygen (1Δg) at concentration level of 2 ... 5 ppb when ice crystals have been exposed to the sun light. In experiments, we used Analyzers of Singlet oxygen and Ozone (produced by JSC "OPTEC") that utilize solid-state chemiluminescence technology. We assumed that the singlet oxygen is formed in the active centers on the surface of ice crystals in the presence or absence of anthropogenic pollutants in the atmosphere. Identified efficiency of heterogeneous reaction of O2 (1Δg) formation suggests the importance of the additional channel O3 + O2 (1Δg) → 2O2 + O (3P) of atmospheric ozone removal comparable with other well known cycles of ozone depletion.
Helical Self-Assembly-Induced Singlet-Triplet Emissive Switching in a Mechanically Sensitive System.
Wu, Hongwei; Zhou, Yunyun; Yin, Liyuan; Hang, Cheng; Li, Xin; Ågren, Hans; Yi, Tao; Zhang, Qing; Zhu, Liangliang
2017-01-18
In nanoscience, chirality has shown a significant ability to tune materials' electronic properties, whereas imposing macrochirality into the regulation of singlet-triplet features of organic optoelectronics remains a challenging research topic. Since the tuning for singlet and triplet excited-state properties in a single π-functional molecule connects to its multicolor luminescent application and potential improvement of internal quantum efficiency, we here report that supramolecular chirality can be employed to toggle the singlet and triplet emissions in a well-designed asterisk-shaped molecule. Employing a hexathiobenzene-based single luminophore as a prototype and functionalizing it with chiral α-lipoiate side groups, we find that helical nanoarchitectures can accordingly form in mixed DMF/H2O solution. On this basis, switching between fluorescence and phosphorescence of the material can be realized upon helical self-assembly and dissociation. Such a behavior can be attributed to a helical-conformation-dependent manipulation of the intersystem crossing. Furthermore, reversible mechanoluminescence of the corresponding solid sample was also observed to rely on an analogous molecular self-assembly alternation. These results can probably provide new visions for the development of next-generation supramolecular chiral functional materials.
Spin-orbit coupling mechanism of singlet oxygen a1Δg quenching by solvent vibrations
Minaev, B. F.
2017-02-01
Degenerate character of the O2(a1Δg) state and of the charge-transfer configurations (CTCs) from solvent to the oxygen open-shell orbitals explains the enhancement of spin-orbit coupling (SOC) which is necessary to overcome spin prohibition during singlet oxygen a1Δg quenching. The former mechanism of non-radiative transition O2(a1Δg) → O2(X3 Σg-) based on electronic energy transfer to the solvent vibrational levels (e-v mechanism) is supplemented here by explicit analysis of SOC effects mediated by solvent and O2 vibrations. The SOC matrix element between one component of the initial electronic excited singlet a1Δg state and the final ground triplet X3 Σg- state in the oxygen moiety is not equal to zero (as in free O2) in the collision complex with solvent molecule (M) when all possible CTCs of the type O2- …M+ are accounted for. Intermolecular configuration interaction between CTC and locally excited states obeys a simple symmetry selection rule which provides finally the SOC matrix element with a guarantee of large orbital rotation around the molecular oxygen axis creating a torque. The CTCs admixtures into the singlet and triplet wave functions in the collision complex O2…M ensure the SOC enhancement inside the O2 moiety and let the spin-prohibited singlet oxygen a1Δg quenching to become effectively allowed in terms of e-v mechanism. In the new model the solvent is not only a passive "sink" for the singlet oxygen excitation energy but serves as an active perturber of the oxygen open shell and finally - of the whole spin dynamics in the collision system.