On the biphoton excitation of the fluorescence of the bacteriochlorophyll molecules of purple photosynthetic bacteria by powerful near IR femto-picosecond pulses

Energy Technology Data Exchange (ETDEWEB)

Borisov, A. Yu., E-mail: borissov@belozersky.msu.ru [Moscow State University, Belozersky Institute of Physicochemical Biology (Russian Federation)

2011-11-15

The authors of a number of experimental works detected nonresonance biphoton excitation of bacteriochlorophyll molecules, which represent the main pigment in the light-absorbing natural 'antenna' complexes of photosynthesizing purple bacteria, by femtosecond IR pulses (1250-1500 nm). They believe that IR quanta excite hypothetic forbidden levels of the pigments of these bacteria in the double frequency range 625-750 nm. We propose and ground an alternative triplet mechanism to describe this phenomenon. According to our hypothesis, the mechanism of biphoton excitation of molecules by IR quanta can manifest itself specifically, through high triplet levels of molecules in the high fields induced by femtosecond-picosecond laser pulses.

Quantum state specific reactant preparation in a molecular beam by rapid adiabatic passage

Science.gov (United States)

Chadwick, Helen; Hundt, P. Morten; van Reijzen, Maarten E.; Yoder, Bruce L.; Beck, Rainer D.

2014-01-01

Highly efficient preparation of molecules in a specific rovibrationally excited state for gas/surface reactivity measurements is achieved in a molecular beam using tunable infrared (IR) radiation from a single mode continuous wave optical parametric oscillator (cw-OPO). We demonstrate that with appropriate focusing of the IR radiation, molecules in the molecular beam crossing the fixed frequency IR field experience a Doppler tuning that can be adjusted to achieve complete population inversion of a two-level system by rapid adiabatic passage (RAP). A room temperature pyroelectric detector is used to monitor the excited fraction in the molecular beam and the population inversion is detected and quantified using IR bleaching by a second IR-OPO. The second OPO is also used for complete population transfer to an overtone or combination vibration via double resonance excitation using two spatially separated RAP processes.

High Excitation Gas and ISM

Science.gov (United States)

Peeters, E.; Martin-Hernandez, N. L.; Rodriguez-Fernandez, N. J.; Tielens, A. G. G. M.

2004-01-01

An overview is given of ISO results on regions of high excitation ISM and gas, i.e. HII regions, the Galactic Centre and Supernovae Remnants. IR emission due to fine-structure lines, molecular hydrogen, silicates, polycyclic aromatic hydrocarbons and dust are summarized, their diagnostic capabilities illustrated and their implications highlighted.

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

Science.gov (United States)

Sun, Jifu; Zhong, Fangfang; Zhao, Jianzhang

2013-07-14

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

Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

Science.gov (United States)

Kwak, Ja Hun; Dagle, Robert; Tustin, Gerald C; Zoeller, Joseph R; Allard, Lawrence F; Wang, Yong

2014-02-06

We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications.

Molecular excited states from the SCAN functional

Science.gov (United States)

Tozer, David J.; Peach, Michael J. G.

2018-06-01

The performance of the strongly constrained and appropriately normed (SCAN) meta-generalised gradient approximation exchange-correlation functional is investigated for the calculation of time-dependent density-functional theory molecular excitation energies of local, charge-transfer and Rydberg character, together with the excited ? potential energy curve in H2. The SCAN results frequently resemble those obtained using a global hybrid functional, with either a standard or increased fraction of exact orbital exchange. For local excitations, SCAN can exhibit significant triplet instability problems, resulting in imaginary triplet excitation energies for a number of cases. The Tamm-Dancoff approximation offers a simple approach to improve the situation, but the excitation energies are still significantly underestimated. Understanding the origin of these (near)-triplet instabilities may provide useful insight into future functional development.

Combined two-photon excitation and d → f energy-transfer in Ir/lanthanide dyads with time-gated selection from a two-component emission spectrum.

Science.gov (United States)

Edkins, Robert M; Sykes, Daniel; Beeby, Andrew; Ward, Michael D

2012-10-14

In a pair of Ir/Eu and Ir/Tb dyads, two-photon excitation of the Ir-phenylpyridine chromophore at 780 nm is followed by partial d → f energy-transfer to give a combination of short-lived Ir-based (blue) and long-lived lanthanide-based (red or green) emission; these components can be selected separately by time-gated detection.

Isotope separation using molecular gases and molecular lasers

International Nuclear Information System (INIS)

Jetter, H.

1975-01-01

Isotope separation using molecular gas and molecular lasers offers several advantages over the alternative method which uses dye lasers and atomic vapour. These advantages are the easy handling of the raw material, the big isotopic shift in the IR, the good efficiency of the laser and the chemical extraction of the excited isotopes. In the case of uranium difficulties arise from the great number of superimposed lines in the absorption band of the UF 6 molecule. Several of these absorption bands were measured using laser spectrometers with ultra-high resolution. The conditions for selective excitation were estimated. (orig.) [de

Relaxation and excitation electronic processes in dielectrics irradiated by ultrafast IR and VUV pulses; Processus electroniques d'excitation et de relaxation dans les solides dielectriques excites par des impulsions IR et XUV ultracourtes

Energy Technology Data Exchange (ETDEWEB)

Gaudin, J

2005-11-15

We studied excitation and relaxation of electrons involved during interaction of visible and VUV femtosecond pulses with dielectrics. The generated population of hot electrons, having energy of few eV to few tens of eV above the bottom of the conduction band, is responsible of phenomena ranging to defect creation to optical breakdown. Owing to two techniques: photoemission and transient photoconductivity we improve the understanding of the The first photoemission experiments deal with dielectrics irradiated by 30 fs IR pulses. The photoemission spectra measured show a large population of electrons which energy rise up to 40 eV. We interpret this result in terms of a new absorption process: direct multi-photons inter-branch transitions. The 2. type of photoemission experiments are time resolved 'pump/probe' investigation. We study the relaxation of electrons excited by a VUV pulses. We used the high order harmonics (HOH) as light sources. We found surprisingly long decay time in the range of ps timescale. Last type of experiments is photoconductivity studies of diamond samples. Using HOH as light source we measure the displacement current induced by excited electrons in the conduction band. Those electrons relax mainly by impact ionisation creating secondary electrons. Hence by probing the number of electrons we were able to measure the efficiency of these relaxation processes. We observe a diminution of this efficiency when the energy of exciting photons is above 20 eV. Owing to Monte-Carlo simulation we interpret this result in terms of band structure effect. (author)

Parallel ferromagnetic resonance and spin-wave excitation in exchange-biased NiFe/IrMn bilayers

Energy Technology Data Exchange (ETDEWEB)

Sousa, Marcos Antonio de, E-mail: marcossharp@gmail.com [Instituto de Física, Universidade Federal de Goiás, Goiânia, 74001-970 (Brazil); Pelegrini, Fernando [Instituto de Física, Universidade Federal de Goiás, Goiânia, 74001-970 (Brazil); Alayo, Willian [Departamento de Física, Universidade Federal de Pelotas, Pelotas, 96010-900 (Brazil); Quispe-Marcatoma, Justiniano; Baggio-Saitovitch, Elisa [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro, 22290-180 (Brazil)

2014-10-01

Ferromagnetic Resonance study of sputtered Ru(7 nm)/NiFe(t{sub FM})/IrMn(6 nm)/Ru(5 nm) exchange-biased bilayers at X and Q-band microwave frequencies reveals the excitation of spin-wave and NiFe resonance modes. Angular variations of the in-plane resonance fields of spin-wave and NiFe resonance modes show the effect of the unidirectional anisotropy, which is about twice larger for the spin-wave mode due to spin pinning at the NiFe/IrMn interface. At Q-band frequency the angular variations of in-plane resonance fields also reveal the symmetry of a uniaxial anisotropy. A modified theoretical model which also includes the contribution of a rotatable anisotropy provides a good description of the experimental results.

Molecular approaches to solar energy conversion: the energetic cost of charge separation from molecular-excited states.

Science.gov (United States)

Durrant, James R

2013-08-13

This review starts with a brief overview of the technological potential of molecular-based solar cell technologies. It then goes on to focus on the core scientific challenge associated with using molecular light-absorbing materials for solar energy conversion, namely the separation of short-lived, molecular-excited states into sufficiently long-lived, energetic, separated charges capable of generating an external photocurrent. Comparisons are made between different molecular-based solar cell technologies, with particular focus on the function of dye-sensitized photoelectrochemical solar cells as well as parallels with the function of photosynthetic reaction centres. The core theme of this review is that generating charge carriers with sufficient lifetime and a high quantum yield from molecular-excited states comes at a significant energetic cost-such that the energy stored in these charge-separated states is typically substantially less than the energy of the initially generated excited state. The role of this energetic loss in limiting the efficiency of solar energy conversion by such devices is emphasized, and strategies to minimize this energy loss are compared and contrasted.

Probing single magnon excitations in Sr₂IrO₄ using O K-edge resonant inelastic x-ray scattering.

Science.gov (United States)

Liu, X; Dean, M P M; Liu, J; Chiuzbăian, S G; Jaouen, N; Nicolaou, A; Yin, W G; Rayan Serrao, C; Ramesh, R; Ding, H; Hill, J P

2015-05-27

Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr2IrO4, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor.

LAD Dissertation Prize Talk: Molecular Collisional Excitation in Astrophysical Environments

Science.gov (United States)

Walker, Kyle M.

2017-06-01

While molecular excitation calculations are vital in determining particle velocity distributions, internal state distributions, abundances, and ionization balance in gaseous environments, both theoretical calculations and experimental data for these processes are lacking. Reliable molecular collisional data with the most abundant species - H2, H, He, and electrons - are needed to probe material in astrophysical environments such as nebulae, molecular clouds, comets, and planetary atmospheres. However, excitation calculations with the main collider, H2, are computationally expensive and therefore various approximations are used to obtain unknown rate coefficients. The widely-accepted collider-mass scaling approach is flawed, and alternate scaling techniques based on physical and mathematical principles are presented here. The most up-to-date excitation data are used to model the chemical evolution of primordial species in the Recombination Era and produce accurate non-thermal spectra of the molecules H2+, HD, and H2 in a primordial cloud as it collapses into a first generation star.

Photoionization of excited molecular states using multiphoton excitation techniques

International Nuclear Information System (INIS)

Dehmer, P.M.; Pratt, S.T.; Dehmer, J.L.

1984-01-01

Photoelectron spectra are reported for three photon resonant, four photon ionization of H 2 via the B 1 Σ + /sub u/, v = 7 (J = 2,4) and C 1 Pi/sub u/, v = 0-4 (J = 1) levels and of N 2 via the o 3 1 Pi/sub u/, v = 1,2, b 1 Pi/sub u/, v = 3-5, and c 1 Pi/sub u/, v = 0 levels. The results reflect both the spectroscopy and the dynamics of photoionization of excited molecular states and are discussed in terms of the selection rules for photoionization and the relative probabilities of photoionization from Rydberg and valence states. In some cases, in accordance with the Franck-Condon principle, the results demonstrate that resonant multiphoton ionization through Rydberg states may be a powerful technique for the production of electronic, vibrational, and rotational state selected ions. However, in other cases, systematic departures from Franck-Condon factors are observed, which reflect the more subtle dynamics of excited state photoionization

Molecular orientation in aligned electrospun polyimide nanofibers by polarized FT-IR spectroscopy.

Science.gov (United States)

Yang, Haoqi; Jiang, Shaohua; Fang, Hong; Hu, Xiaowu; Duan, Gaigai; Hou, Haoqing

2018-07-05

Quantitative explanation on the improved mechanical properties of aligned electrospun polyimide (PI) nanofibers as the increased imidization temperatures is highly required. In this work, polarized FT-IR spectroscopy is applied to solve this problem. Based on the polarized FT-IR spectroscopy and the molecular model in the fibers, the length of the repeat unit of PI molecule, the angle between the fiber axis and the symmetric stretching direction of carbonyl group on the imide ring, and the angle between the PI molecular axis and fiber axis are all investigated. The Mark-Howink equation is used to calculate the number-average molar mass of PI molecules. The orientation states of PI molecules in the electrospun nanofibers are studied from the number-average molar mass of PI molecules and the average fiber diameter. Quantitative analysis of the orientation factor of PI molecules in the electrospun nanofibers is performed by polarized FT-IR spectroscopy. Copyright © 2018 Elsevier B.V. All rights reserved.

Photoionization of excited molecular states using multiphoton excitation techniques

International Nuclear Information System (INIS)

Dehmer, P.M.; Pratt, S.T.; Dehmer, J.L.

1984-01-01

Photoelectron spectra are reported for three photon resonant, four photon ionization of H 2 via the B 1 Σ/sub u/ + , v = 7 (J = 2,4) and C 1 π/sub u'/, v = 0-4 (J = 1) levels and of N 2 via the o 3 1 π/sub u'/, v = 1,2, b 1 π/sub u'/, v = 3-5, and c 1 π/sub u'/, v = 0 levels. The results reflect both the spectroscopy and the dynamics of photoionization of excited molecular states and are discussed in terms of the selection rules for photoionization and the relative probabilities of photoionization from Rydberg and valence states. In some cases, in accordance with the Franck-Condon principle, the results demonstrate that resonant multiphoton ionization through Rydberg states may be a powerful technique for the production of electronic, vibrational, and rotational state selected ions. However, in other cases, systematic departures from Franck-Condon factors are observed, which reflect the more subtle dynamics of excited state photoionization. 23 references, 6 figures, 2 tables

Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states.

Science.gov (United States)

Soliman, Ahmed M; Fortin, Daniel; Zysman-Colman, Eli; Harvey, Pierre D

2012-04-13

Trans- dichlorobis(tri-n-butylphosphine)platinum(II) reacts with bis(2- phenylpyridinato)-(5,5'-diethynyl-2,2'-bipyridine)iridium(III) hexafluorophosphate to form the luminescent conjugated polymer poly[trans-[(5,5'-ethynyl-2,2'-bipyridine)bis(2- phenylpyridinato)-iridium(III)]bis(tri-n-butylphosphine)platinum(II)] hexafluorophosphate ([Pt]-[Ir])n. Gel permeation chromatography indicates a degree of polymerization of 9 inferring the presence of an oligomer. Comparison of the absorption and emission band positions and their temperature dependence, emission quantum yields, and lifetimes with those for models containing only the [Pt] or the [Ir] units indicates hybrid excited states including features from both chromophores. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Emission spectroscopic studies on dynamics of molecular excitation and dissociation by controlled electron impact

International Nuclear Information System (INIS)

Ogawa, Teiichiro

1986-01-01

Emission spectrum by controlled electron impact has been a successful technique for the investigation of molecular dynamics. (1) Molecular excitation. Aromatic molecules give an optical emission similar to fluorescence. However, as is shown by the vibrational structure and the electron energy dependence of benzene emission, its excitation process is not necessarily optical. Some aliphatic molecules also exhibit an emission band at the ultraviolet region. (2) Molecular dissociation. Analysis of the Doppler profile, the threshold energy, the excitation function and the isotope effect of the atomic emission produced in electron-molecule collisions has clarified the dynamics of the molecular dissociation. Especially the Doppler profile has given the translational energy distribution of the fragment atom, which is very useful to disclose the potential energy curve. Its angular dependence has recently found to allow determination of the symmetry of the intermediate excited state and the magnetic sublevel distribution of the fragment atom. These finding has revealed detailed state-to-state dynamics of the molecular dissociation. (author)

HERSCHEL-PACS OBSERVATIONS OF FAR-IR CO LINE EMISSION IN NGC 1068: HIGHLY EXCITED MOLECULAR GAS IN THE CIRCUMNUCLEAR DISK

Energy Technology Data Exchange (ETDEWEB)

Hailey-Dunsheath, S.; Sturm, E.; Gracia-Carpio, J.; Davies, R.; Poglitsch, A.; Contursi, A.; Genzel, R.; Lutz, D.; Tacconi, L.; De Jong, J. A. [Max-Planck-Institut fuer extraterrestrische Physik, Postfach 1312, D-85741 Garching (Germany); Fischer, J. [Naval Research Laboratory, Remote Sensing Division, 4555 Overlook Ave SW, Washington, DC 20375 (United States); Sternberg, A.; Mark, D. [Sackler School of Physics and Astronomy, Tel Aviv University, Ramat Aviv 69978 (Israel); Gonzalez-Alfonso, E. [Departamento de Fisica, Universidad de Alcala de Henares, 28871 Alcala de Henares, Madrid (Spain); Veilleux, S. [Department of Astronomy, University of Maryland, College Park, MD 20742 (United States); Verma, A., E-mail: shd@astro.caltech.edu [Department of Astrophysics, Oxford University, Oxford OX1 3RH (United Kingdom)

2012-08-10

We report the detection of far-IR CO rotational emission from the prototypical Seyfert 2 galaxy NGC 1068. Using Herschel-PACS, we have detected 11 transitions in the J{sub upper} = 14-30 (E{sub upper}/k{sub B} = 580-2565 K) range, all of which are consistent with arising from within the central 10'' (700 pc). The detected transitions are modeled as arising from two different components: a moderate-excitation (ME) component close to the galaxy systemic velocity and a high-excitation (HE) component that is blueshifted by {approx}80 km s{sup -1}. We employ a large velocity gradient model and derive n{sub H2} {approx} 10{sup 5.6} cm{sup -3}, T{sub kin} {approx} 170 K, and M{sub H2} {approx} 10{sup 6.7} M{sub Sun} for the ME component and n{sub H2} {approx} 10{sup 6.4} cm{sup -3}, T{sub kin} {approx} 570 K, and M{sub H2} {approx} 10{sup 5.6} M{sub Sun} for the HE component, although for both components the uncertainties in the density and mass are {+-}(0.6-0.9) dex. Both components arise from denser and possibly warmer gas than traced by low-J CO transitions, and the ME component likely makes a significant contribution to the mass budget in the nuclear region. We compare the CO line profiles with those of other molecular tracers observed at higher spatial and spectral resolution and find that the ME transitions are consistent with these lines arising in the {approx}200 pc diameter ring of material traced by H{sub 2} 1-0 S(1) observations. The blueshift of the HE lines may also be consistent with the bluest regions of this H{sub 2} ring, but a better kinematic match is found with a clump of infalling gas {approx}40 pc north of the active galactic nucleus (AGN). We consider potential heating mechanisms and conclude that X-ray- or shock heating of both components is viable, while far-UV heating is unlikely. We discuss the prospects of placing the HE component near the AGN and conclude that while the moderate thermal pressure precludes an association with the

IL 6: 2D-IR spectroscopy: chemistry and biophysics in real time

International Nuclear Information System (INIS)

Bredenbeck, Jens

2010-01-01

Pulsed multidimensional experiments, daily business in the field of NMR spectroscopy, have been demonstrated only relatively recently in IR spectroscopy. Similar as nuclear spins in multidimensional NMR, molecular vibrations are employed in multidimensional IR experiments as probes of molecular structure and dynamics, albeit with femtosecond time resolution. Different types of multidimensional IR experiments have been implemented, resembling basic NMR experiments such as NOESY, COSY and EXSY. In contrast to one-dimensional linear spectroscopy, such multidimensional experiments reveal couplings and correlations of vibrations, which are closely linked to molecular structure and its change in time. The use of mixed IR/VIS pulse sequences further extends the potential of multidimensional IR spectroscopy, enabling studies of ultrafast non-equilibrium processes as well as surface specific, highly sensitive experiments. A UV/VIS pulse preceding the IR pulse sequence can be used to prepare the system under study in a non-equilibrium state. 2D-IR snapshots of the evolving non-equilibrium system are then taken, for example during a photochemical reaction or during the photo-cycle of a light sensitive protein. Preparing the system in a non-equilibrium state by UV/Vis excitation during the IR pulse sequence allows for correlating states of reactant and product of the light triggered process via their 2D-IR cross peaks - a technique that has been used to map the connectivity between different binding sites of a ligand as it migrates through a protein. Introduction of a non-resonant VIS pulse at the end of the IR part of the experiment allows to selectively up-convert the infrared signal of interfacial molecules to the visible spectral range by sum frequency generation. In this way, femtosecond interfacial 2D-IR spectroscopy can be implemented, achieving sub-monolayer sensitivity. (author)

Exploring the vibrational fingerprint of the electronic excitation energy via molecular dynamics

International Nuclear Information System (INIS)

Deyne, Andy Van Yperen-De; Pauwels, Ewald; Ghysels, An; Waroquier, Michel; Van Speybroeck, Veronique; Hemelsoet, Karen; De Meyer, Thierry; De Clerck, Karen

2014-01-01

A Fourier-based method is presented to relate changes of the molecular structure during a molecular dynamics simulation with fluctuations in the electronic excitation energy. The method implies sampling of the ground state potential energy surface. Subsequently, the power spectrum of the velocities is compared with the power spectrum of the excitation energy computed using time-dependent density functional theory. Peaks in both spectra are compared, and motions exhibiting a linear or quadratic behavior can be distinguished. The quadratically active motions are mainly responsible for the changes in the excitation energy and hence cause shifts between the dynamic and static values of the spectral property. Moreover, information about the potential energy surface of various excited states can be obtained. The procedure is illustrated with three case studies. The first electronic excitation is explored in detail and dominant vibrational motions responsible for changes in the excitation energy are identified for ethylene, biphenyl, and hexamethylbenzene. The proposed method is also extended to other low-energy excitations. Finally, the vibrational fingerprint of the excitation energy of a more complex molecule, in particular the azo dye ethyl orange in a water environment, is analyzed

MOLECULAR BEAM STUDIES OF IR LASER INDUCED MULTIPHOTON DISSOCIATION AND VIBRATIONAL PREDISSOCIATION

Energy Technology Data Exchange (ETDEWEB)

Lee, Yuan T.; Shen, Y. Ron

1980-06-01

The advancement of crossed molecular beam methods, modern spectroscopy and laser technology allows us to observe chemical reactions on atomic and molecular levels in great detail. After a brief history of crossed molecular beams studies, the author describes and discusses the universal molecular beam apparatus and gives examples of crossed molecular beam studies. The crossed beam technique is compared to other techniques used to provide microscopic information on reaction dynamics. Application of crossed laser and molecular beam studies to the problem of IR multiphoton dissociation of polyatomic molecules is discussed. Study of vibrational predissociation of hydrogen-bonded and van der Waals molecular clusters are discussed. Future cases that the author considers worth pursuing that could benefit from the collisionless environment of molecular beams are enumerated.

Excited state dynamics & optical control of molecular motors

Science.gov (United States)

Wiley, Ted; Sension, Roseanne

2014-03-01

Chiral overcrowded alkenes are likely candidates for light driven rotary molecular motors. At their core, these molecular motors are based on the chromophore stilbene, undergoing ultrafast cis/trans photoisomerization about their central double bond. Unlike stilbene, the photochemistry of molecular motors proceeds in one direction only. This unidirectional rotation is a result of helicity in the molecule induced by steric hindrance. However, the steric hindrance which ensures unidirectional excited state rotation, has the unfortunate consequence of producing large ground state barriers which dramatically decrease the overall rate of rotation. These molecular scale ultrafast motors have only recently been studied by ultrafast spectroscopy. Our lab has studied the photochemistry and photophysics of a ``first generation'' molecular motor with UV-visible transient absorption spectroscopy. We hope to use optical pulse shaping to enhance the efficiency and turnover rate of these molecular motors.

Probing single magnon excitations in Sr2IrO4 using O K-edge resonant inelastic x-ray scattering

International Nuclear Information System (INIS)

Liu, X; Ding, H; Dean, M P M; Yin, W G; Hill, J P; Liu, J; Ramesh, R; Chiuzbăian, S G; Jaouen, N; Nicolaou, A; Serrao, C Rayan

2015-01-01

Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin–orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr 2 IrO 4 , where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor. (fast track communication)

Electron collisions and internal excitation in stored molecular ion beams

International Nuclear Information System (INIS)

Buhr, H.

2006-01-01

In storage ring experiments the role, which the initial internal excitation of a molecular ion can play in electron collisions, and the effect of these collisions on the internal excitation are investigated. Dissociative recombination (DR) and inelastic and super-elastic collisions are studied in the system of He + 2 . The DR rate coefficient at low energies depends strongly on the initial vibrational excitation in this system. Therefore changes in the DR rate coefficient are a very sensitive probe for changes in the vibrational excitation in He + 2 , which is used to investigate the effects of collisions with electrons and residual gas species. The low-energy DR of HD + is rich with resonances from the indirect DR process, when certain initial rotational levels in the molecular ion are coupled to levels in neutral Rydberg states lying below the ion state. Using new procedures for high-resolution electron-ion collision spectroscopy developed here, these resonances in the DR cross section can be measured with high energy sensitivity. This allows a detailed comparison with results of a MQDT calculation in an effort to assign some or all of the resonances to certain intermediate Rydberg levels. (orig.)

Electron collisions and internal excitation in stored molecular ion beams

Energy Technology Data Exchange (ETDEWEB)

Buhr, H.

2006-07-26

In storage ring experiments the role, which the initial internal excitation of a molecular ion can play in electron collisions, and the effect of these collisions on the internal excitation are investigated. Dissociative recombination (DR) and inelastic and super-elastic collisions are studied in the system of He{sup +}{sub 2}. The DR rate coefficient at low energies depends strongly on the initial vibrational excitation in this system. Therefore changes in the DR rate coefficient are a very sensitive probe for changes in the vibrational excitation in He{sup +}{sub 2}, which is used to investigate the effects of collisions with electrons and residual gas species. The low-energy DR of HD{sup +} is rich with resonances from the indirect DR process, when certain initial rotational levels in the molecular ion are coupled to levels in neutral Rydberg states lying below the ion state. Using new procedures for high-resolution electron-ion collision spectroscopy developed here, these resonances in the DR cross section can be measured with high energy sensitivity. This allows a detailed comparison with results of a MQDT calculation in an effort to assign some or all of the resonances to certain intermediate Rydberg levels. (orig.)

Field-dependent molecular ionization and excitation energies: Implications for electrically insulating liquids

Directory of Open Access Journals (Sweden)

N. Davari

2014-03-01

Full Text Available The molecular ionization potential has a relatively strong electric-field dependence as compared to the excitation energies which has implications for electrical insulation since the excited states work as an energy sink emitting light in the UV/VIS region. At some threshold field, all the excited states of the molecule have vanished and the molecule is a two-state system with the ground state and the ionized state, which has been hypothesized as a possible origin of different streamer propagation modes. Constrained density-functional theory is used to calculate the field-dependent ionization potential of different types of molecules relevant for electrically insulating liquids. The low singlet-singlet excitation energies of each molecule have also been calculated using time-dependent density functional theory. It is shown that low-energy singlet-singlet excitation of the type n → π* (lone pair to unoccupied π* orbital has the ability to survive at higher fields. This type of excitation can for example be found in esters, diketones and many color dyes. For alkanes (as for example n-tridecane and cyclohexane on the other hand, all the excited states, in particular the σ → σ* excitations vanish in electric fields higher than 10 MV/cm. Further implications for the design of electrically insulating dielectric liquids based on the molecular ionization potential and excitation energies are discussed.

Relaxation and excitation electronic processes in dielectrics irradiated by ultrafast IR and VUV pulses

International Nuclear Information System (INIS)

Gaudin, J.

2005-11-01

We studied excitation and relaxation of electrons involved during interaction of visible and VUV femtosecond pulses with dielectrics. The generated population of hot electrons, having energy of few eV to few tens of eV above the bottom of the conduction band, is responsible of phenomena ranging to defect creation to optical breakdown. Owing to two techniques: photoemission and transient photoconductivity we improve the understanding of the The first photoemission experiments deal with dielectrics irradiated by 30 fs IR pulses. The photoemission spectra measured show a large population of electrons which energy rise up to 40 eV. We interpret this result in terms of a new absorption process: direct multi-photons inter-branch transitions. The 2. type of photoemission experiments are time resolved 'pump/probe' investigation. We study the relaxation of electrons excited by a VUV pulses. We used the high order harmonics (HOH) as light sources. We found surprisingly long decay time in the range of ps timescale. Last type of experiments is photoconductivity studies of diamond samples. Using HOH as light source we measure the displacement current induced by excited electrons in the conduction band. Those electrons relax mainly by impact ionisation creating secondary electrons. Hence by probing the number of electrons we were able to measure the efficiency of these relaxation processes. We observe a diminution of this efficiency when the energy of exciting photons is above 20 eV. Owing to Monte-Carlo simulation we interpret this result in terms of band structure effect. (author)

Studies of isotopic effects in the excited electronic states of molecular systems

International Nuclear Information System (INIS)

1982-01-01

Rare gas halogen (RGH) lasers serve as convenient tools for a range of photophysical processes which exhibit isotope effects. This document summarizes progress in the production of molecular systems in their electronic excited states with the aid of RGH lasers, and the various isotopic effects one can study under these conditions. We conclude that the basic physical mechanisms involved in the isotopically sensitive characteristics of excited molecular electronic states are sufficiently selective to be useful in both the detection and separation of many atomic materials

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

DEFF Research Database (Denmark)

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

2011-01-01

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

Magnetic structure and excitation spectrum of the hyperhoneycomb Kitaev magnet β -Li2IrO3

Science.gov (United States)

Ducatman, Samuel; Rousochatzakis, Ioannis; Perkins, Natalia B.

2018-03-01

We present a theoretical study of the static and dynamical properties of the three-dimensional, hyperhoneycomb Kitaev magnet β -Li2IrO3 . We argue that the observed incommensurate order can be understood in terms of a long-wavelength twisting of a nearby commensurate period-3 state, with the same key qualitatively features. The period-3 state shows very different structure when either the Kitaev interaction K or the off-diagonal exchange anisotropy Γ is dominant. A comparison of the associated static spin structure factors with reported scattering experiments in zero and finite fields gives strong evidence that β -Li2IrO3 lies in the regime of dominant Kitaev coupling, and that the Heisenberg exchange J is much weaker than both K and Γ . Our predictions for the magnon excitation spectra, the dynamical spin structure factors, and their polarization dependence provide additional distinctive fingerprints that can be checked experimentally.

Molecular orbital calculations of the unpaired electron distribution and electric field gradients in divalent paramagnetic Ir complexes

International Nuclear Information System (INIS)

Nogueira, S.R.; Vugman, N.V.; Guenzburger, D.

1988-01-01

Semi-empirical Molecular Orbital calculations were performed for the paramagnetic complex ions [Ir(CN) 5 ] 3- , [Ir(CN) 5 Cl] 4- and [Ir(CN) 4 Cl 2 ] 4- . Energy levels schemes and Mulliken-type populations were obtained. The distribution of the unpaired spin over the atoms in the complexes was derived, and compared to data obtained from Electron Paramagnetic Resonance spectra with the aid of a Ligand Field model. The electric field gradients at the Ir nucleus were calculated and compared to experiment. The results are discussed in terms of the chemical bonds formed by Ir and the ligands. (author) [pt

Range-separated density-functional theory for molecular excitation energies

International Nuclear Information System (INIS)

Rebolini, E.

2014-01-01

Linear-response time-dependent density-functional theory (TDDFT) is nowadays a method of choice to compute molecular excitation energies. However, within the usual adiabatic semi-local approximations, it is not able to describe properly Rydberg, charge-transfer or multiple excitations. Range separation of the electronic interaction allows one to mix rigorously density-functional methods at short range and wave function or Green's function methods at long range. When applied to the exchange functional, it already corrects most of these deficiencies but multiple excitations remain absent as they need a frequency-dependent kernel. In this thesis, the effects of range separation are first assessed on the excitation energies of a partially-interacting system in an analytic and numerical study in order to provide guidelines for future developments of range-separated methods for excitation energy calculations. It is then applied on the exchange and correlation TDDFT kernels in a single-determinant approximation in which the long-range part of the correlation kernel vanishes. A long-range frequency-dependent second-order correlation kernel is then derived from the Bethe-Salpeter equation and added perturbatively to the range-separated TDDFT kernel in order to take into account the effects of double excitations. (author)

Spectroscopic [FT-IR and FT-Raman] and molecular modeling (MM) study of benzene sulfonamide molecule using quantum chemical calculations

Science.gov (United States)

Vinod, K. S.; Periandy, S.; Govindarajan, M.

2016-07-01

The spectroscopic and molecular modeling (MM) study includes, FT-IR, FT-Raman and 13C NMR and 1H NMR spectra of the Benzene sulfonamide were recorded for the analysis. The observed experimental and theoretical frequencies (IR and Raman) were assigned according to their distinctive region. The present study of this title molecule have been carried out by hybrid computational calculations of HF and DFT (B3LYP) methods with 6-311+G(d,p) and 6-311++G(d,p) basis sets and the corresponding results are tabulated. The structural modifications of the compound due to the substitutions of NH2 and SO2 were investigated. The minimum energy conformers of the compound were studied using conformational analysis. The alternations of the vibrational pattern of the base structure related to the substitutions were analyzed. The thermodynamic parameters (such as zero-point vibrational energy, thermal energy, specific heat capacity, rotational constants, entropy, and dipole moment) of Benzene sulfonamide have been calculated. The donor acceptor interactions of the compound and the corresponding UV transitions are found out using NBO analysis. The NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts related to TMS were compared. A quantum computational study on the electronic and optical properties absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by HF and DFT methods. The energy gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand group. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures were calculated in gas phase and

Investigation of pollutant gases with molecular absorption spectroscopy

International Nuclear Information System (INIS)

Izairi, N; Ajredini, F.; Shehabi, M.

2011-01-01

This paper contains the molecular absorption spectroscopic investigation on environmental pollution by many pollutants. For this purpose a laser absorption spectroscopy at 630 nm wavelength has been applied to excite the molecular spectra in order to identify the presence of main gas pollutants. The following was the experimental procedure. Preliminary the presence of pollutants was identified. The gas champions were taken in live environment, in Tetovo streets where cars moved, and in some points in Tetovo suburbia, during different periods of the day. A special civet, part of the apparatus, has been filled by environmental air, and latter, put into the apparatus. A laser beam pulse passes throughout absorbing gas medium in the civet to excite the gas, and the absorbing spectra were automatically registered. The molecular band spectra registration has been performed by an FT-IR Spectrometer (Spectrum BX FT-IR Perkin Elmer). For this purpose the measurements were focused in spectral region of 2075 cm -1 to 2384 cm -1 for CO 2 and CO bands investigation. The importance of such measurements is to investigate the spectral properties of absorption spectra and molecular structure, and for monitoring the environmental pollution. (Author)

Nonlinear excitations in two-dimensional molecular structures with impurities

DEFF Research Database (Denmark)

Gaididei, Yuri Borisovich; Rasmussen, Kim; Christiansen, Peter Leth

1995-01-01

We study the nonlinear dynamics of electronic excitations interacting with acoustic phonons in two-dimensional molecular structures with impurities. We show that the problem is reduced to the nonlinear Schrodinger equation with a varying coefficient. The latter represents the influence...... of the impurity. Transforming the equation to the noninertial frame of reference coupled with the center of mass we investigate the soliton behavior in the close vicinity of the impurity. With the help of the lens transformation we show that the soliton width is governed by an Ermakov-Pinney equation. We also...... excitations. Analytical results are in good agreement with numerical simulations of the nonlinear Schrodinger equation....

Nanoantennas for surface enhanced infrared spectroscopy: Effects of interaction and higher order resonant excitations

Directory of Open Access Journals (Sweden)

J. Aizpurua

2011-09-01

Full Text Available The sensitivity in surface enhanced infrared spectroscopy (SEIRS strongly depends on where the resonant excitation is spectrally located compared to the molecular vibration that is to be enhanced. In this contribution, we study the effect of coupling in the electromagnetic properties of 2D gold nanorod arrays in the IR. We also study the SEIRS activity of higher order resonant excitations in long nanoantennas to identify polaritonic signals of a supporting SiO2 layer with nanometer thickness (3 nm on a silicon substrate.

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

Science.gov (United States)

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

2015-12-21

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

Collision dynamics of methyl radicals and highly vibrationally excited molecules using crossed molecular beams

International Nuclear Information System (INIS)

Chu, P.M.Y.

1991-10-01

The vibrational to translational (V→T) energy transfer in collisions between large highly vibrationally excited polyatomics and rare gases was investigated by time-of-flight techniques. Two different methods, UV excitation followed by intemal conversion and infrared multiphoton excitation (IRMPE), were used to form vibrationally excited molecular beams of hexafluorobenzene and sulfur hexafluoride, respectively. The product translational energy was found to be independent of the vibrational excitation. These results indicate that the probability distribution function for V→T energy transfer is peaked at zero. The collisional relaxation of large polyatomic molecules with rare gases most likely occurs through a rotationally mediated process. Photodissociation of nitrobenzene in a molecular beam was studied at 266 nm. Two primary dissociation channels were identified including simple bond rupture to produce nitrogen dioxide and phenyl radical and isomerization to form nitric oxide and phenoxy radical. The time-of-flight spectra indicate that simple bond rupture and isomerization occurs via two different mechanisms. Secondary dissociation of the phenoxy radicals to carbon monoxide and cyclopentadienyl radicals was observed as well as secondary photodissociation of phenyl radical to give H atom and benzyne. A supersonic methyl radical beam source is developed. The beam source configuration and conditions were optimized for CH 3 production from the thermal decomposition of azomethane. Elastic scattering of methyl radical and neon was used to differentiate between the methyl radicals and the residual azomethane in the molecular beam

Molecular hydrogen line ratios in four regions of shock-excited gas

International Nuclear Information System (INIS)

Burton, M.G.

1989-01-01

Five emission lines of molecular hydrogen, with wavelengths in the ranges of 2.10-2.25 and 3.80-3.85 μm, have been observed in four objects of different type in which the line emission is believed to be excited by shocks. (author)

Molecular and excited state properties of isomeric scarlet disperse dyes

Science.gov (United States)

Lim, Jihye; Szymczyk, Malgorzata; Mehraban, Nahid; Ding, Yi; Parrillo-Chapman, Lisa; El-Shafei, Ahmed; Freeman, Harold S.

2018-06-01

This work was part of an investigation aimed at characterizing the molecular and excited state properties of currently available disperse dyes developed to provide stability to extensive sunlight exposures when adsorbed on poly(ethylene terephthalate) (PET) fibers. Having completed the characterization of yellow, magenta, and cyan disperse dyes for PET-based fabrics used outdoors, our attention turned to the colors designed to enhance the color gamut of a standard 4-member (cyan/yellow/magenta/black) color set. The present study pertained specifically to the characterization of commercially available scarlet dyes. In this regard, HPLC analysis showed that a scarlet product used for PET coloration was mainly a 70/30 mixture of dyes, and the use of HRMS and single crystal X-ray diffraction analyses indicated that these two dyes were azo compounds derived from isomeric pyridine-based couplers which differed in the location of the primary amino (sbnd NH2) and anilino (sbnd NHPh) groups attached to the pyridine ring. One dye structure has the sbnd NHPh group para to the azo group (Sc2), while the other has that group in the ortho position (Sc3). The presence of either ortho substituent provides photostabilization through intramolecular H-bonding with the azo moiety. Further, results from molecular modeling studies showed that the lower excited state oxidation potential of Sc3 relative to that of Sc2 allows Sc3 to function as an energy quencher for the excited state of Sc2 - through thermodynamically favorable electron transfer.

Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states

Energy Technology Data Exchange (ETDEWEB)

Nelson, Tammie [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Naumov, Artem [Skolkovo Institute of Science and Technology, Moscow 143026 (Russian Federation); Fernandez-Alberti, Sebastian [Universidad Nacional de Quilmes, Roque Saenz Pea 352, B1876BXD Bernal (Argentina); Tretiak, Sergei, E-mail: serg@lanl.gov [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

2016-12-20

The simulation of nonadiabatic dynamics in extended molecular systems involving hundreds of atoms and large densities of states is particularly challenging. Nonadiabatic coupling terms (NACTs) represent a significant numerical bottleneck in surface hopping approaches. Rather than using unreliable NACT cutting schemes, here we develop “on-the-fly” state limiting methods to eliminate states that are no longer essential for the non-radiative relaxation dynamics as a trajectory proceeds. We propose a state number criteria and an energy-based state limit. The latter is more physically relevant by requiring a user-imposed energy threshold. For this purpose, we introduce a local kinetic energy gauge by summing contributions from atoms within the spatial localization of the electronic wavefunction to define the energy available for upward hops. The proposed state limiting schemes are implemented within the nonadiabatic excited-state molecular dynamics framework to simulate photoinduced relaxation in poly-phenylene vinylene (PPV) and branched poly-phenylene ethynylene (PPE) oligomers for benchmark evaluation.

Dynamic coherence in excitonic molecular complexes under various excitation conditions

Energy Technology Data Exchange (ETDEWEB)

Chenu, Aurélia; Malý, Pavel; Mančal, Tomáš, E-mail: mancal@karlov.mff.cuni.cz

2014-08-17

Highlights: • Dynamic coherence does not improve energy transfer efficiency in natural conditions. • Photo-induced quantum jumps are discussed in classical context. • Natural time scale of a light excitation event is identified. • Coherence in FMO complex averages out under excitation by neighboring antenna. • This result is valid even in absence of dissipation. - Abstract: We investigate the relevance of dynamic quantum coherence in the energy transfer efficiency of molecular aggregates. We derive the time evolution of the density matrix for an open quantum system excited by light or by a neighboring antenna. Unlike in the classical case, the quantum description does not allow for a formal decomposition of the dynamics into sudden jumps in an observable quantity – an expectation value. Rather, there is a natural finite time-scale associated with the excitation process. We propose a simple experiment to test the influence of this time scale on the yield of photosynthesis. We demonstrate, using typical parameters of the Fenna–Matthews–Olson (FMO) complex and a typical energy transfer rate from the chlorosome baseplate, that dynamic coherences are averaged out in the complex even when the FMO model is completely free of all dissipation and dephasing.

Molecular vibrational investigation [FT-IR, FT-Raman, UV-Visible and NMR] on Bis(thiourea) Nickel chloride using HF and DFT calculations

Science.gov (United States)

Anand, S.; Sundararajan, R. S.; Ramachandraraja, C.; Ramalingam, S.; Durga, R.

2015-03-01

In the present research work, the FT-IR, FT-Raman spectra of the Bis(thiourea) Nickel chloride (BTNC) were recorded and analyzed. The observed fundamental frequencies in finger print and functional group regions were assigned according to their uniqueness region. The computational calculations were carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The present organo-metallic compound was made up of covalent and coordination covalent bonds. The modified vibrational pattern of the complex molecule associated with ligand group was analyzed. Furthermore, the 13C NMR and 1H NMR spectral data were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP/6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A investigation on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed.

Invited Article: Multiple-octave spanning high-energy mid-IR supercontinuum generation in bulk quadratic nonlinear crystals

Directory of Open Access Journals (Sweden)

Binbin Zhou

2016-08-01

Full Text Available Bright and broadband coherent mid-IR radiation is important for exciting and probing molecular vibrations. Using cascaded nonlinearities in conventional quadratic nonlinear crystals like lithium niobate, self-defocusing near-IR solitons have been demonstrated that led to very broadband supercontinuum generation in the visible, near-IR, and short-wavelength mid-IR. Here we conduct an experiment where a mid-IR crystal is pumped in the mid-IR. The crystal is cut for noncritical interaction, so the three-wave mixing of a single mid-IR femtosecond pump source leads to highly phase-mismatched second-harmonic generation. This self-acting cascaded process leads to the formation of a self-defocusing soliton at the mid-IR pump wavelength and after the self-compression point multiple octave-spanning supercontinua are observed. The results were recorded in a commercially available crystal LiInS2 pumped in the 3-4 μm range with 85 fs 50 μJ pulse energy, with the broadest supercontinuum covering 1.6-7.0 μm. We measured up 30 μJ energy in the supercontinuum, and the energy promises to scale favorably with an increased pump energy. Other mid-IR crystals can readily be used as well to cover other pump wavelengths and target other supercontinuum wavelength ranges.

Plasmon assisted control of photo-induced excitation energy transfer in a molecular chain

Science.gov (United States)

Wang, Luxia; May, Volkhard

2017-08-01

The strong and ultrafast laser pulse excitation of a molecular chain in close vicinity to a spherical metal nano-particle (MNP) is studied theoretically. Due to local-field enhancement around the MNP, pronounced excited-state formation has to be expected for the part of the chain which is in proximity to the MNP. Here, the description of this phenomenon will be based on a uniform quantum theory of the MNP-molecule system. It accounts for local-field effects due to direct consideration of the strong excitation energy transfer coupling between the MNP and the various molecules. The molecule-MNP distances are chosen in such a way as to achieve a correct description of the MNP via dipole-plasmon excitations. Short plasmon life-times are incorporated in the framework of a density matrix approach. By extending earlier work the present description allows for multi-exciton formation and multiple dipole-plasmon excitation. The region of less intense and not-too-short optical excitation is identified as being best suited for excitation energy localization in the chain.

Spectroscopy and reactions of vibrationally excited transient molecules

Energy Technology Data Exchange (ETDEWEB)

Dai, H.L. [Univ. of Pennsylvania, Philadelphia (United States)

1993-12-01

Spectroscopy, energy transfer and reactions of vibrationally excited transient molecules are studied through a combination of laser-based excitation techniques and efficient detection of emission from the energized molecules with frequency and time resolution. Specifically, a Time-resolved Fourier Transform Emission Spectroscopy technique has been developed for detecting dispersed laser-induced fluorescence in the IR, visible and UV regions. The structure and spectroscopy of the excited vibrational levels in the electronic ground state, as well as energy relaxation and reactions induced by specific vibronic excitations of a transient molecule can be characterized from time-resolved dispersed fluorescence in the visible and UV region. IR emissions from highly vibrational excited levels, on the other hand, reveal the pathways and rates of collision induced vibrational energy transfer.

Proposals of electronic-vibrational energy relaxation studies by using laser pulses synchronized with IR-SR pulses

International Nuclear Information System (INIS)

Nakagawa, Hideyuki

2000-01-01

Synchrotron radiation is expected to be the sharp infrared light source for the advanced experiments on IR and FIR spectroscopy in wide research fields. Especially, synchronized use of SR with VIS and/or UV laser light is to be a promising technique for the research on the dynamical properties of the photo-excited states in condensed materials. Some proposals are attempted for high resolution IR spectroscopy to elucidate fine interaction of molecular ions in crystalline solids with their environmental field and for time-resolved IR spectroscopic studies on the electronic and vibrational energy relaxation by using laser pulses synchronized with IR-SR pulses. Several experimental results are presented in relevance to the subjects; on high-resolution FTIR spectra of cyanide ions and metal cyanide complexes in cadmium halide crystals, on the energy up-conversion process among the vibrational levels of cyanide ions in alkali halide crystals, and on the electronic-to-vibrational energy conversion process in metal cyanide complexes. (author)

Measurement and analysis of the excitation function and isomeric cross section ratios for α-induced reaction on Ir, Au, Re and Ta nuclei

International Nuclear Information System (INIS)

Ismail, M.

1998-01-01

Excitation functions and a few isomeric cross section ratios for production of (1) 192 Au, 193 Au, 194 Au, 195 Au and 192 Ir nuclides in α-induced reactions on 191,193 Ir, (2) 197 Tl, 197m Hg, 198m.g Tl, 199 Tl and 200 Tl nuclides in α-induced reaction in 197 Au and (3) 183 Re and 184m.g Re nuclides in α-induced reaction in 181 Ta and 185 Re are obtained from the measurements of the residual activities by the conventional stacked-foils technique from threshold to 50 MeV. The excitation function and isomeric cross section ratios for nuclear reaction 181 Ta (α,n) 184m.g Re are compared with the theoretical calculation using the code Stapre which is based on exciton model for pre-equilibrium phase and Hauser-Feshbach formalism taking angular momentum and parity into account for the equilibrium phase of the nuclear reaction. All other experimental excitation functions are compared with the calculations considering equilibrium as well as pre-equilibrium reaction mechanism according to the geometry dependent hybrid (GDH) model and hybrid model of Blann using the code Alice/91. The high energy part of the excitation functions are dominated by pre-equilibrium reaction mechanism whereas the low energy parts are dominated by equilibrium evaporation with its characteristic peak. The GDH model provides a potentially better description of the physical process (i.e. a higher probability for peripheral collisions to undergo precompound decay than for central collisions) compared to hybrid model. However in the energy range of present measurement most of the excitation functions are fitted reasonably well by both GDH model and hybrid model with initial exciton number N 0 =4 (N n =2, N p =2, N h =0). Barring a few reactions we have found the overall agreement between theory and experiment is reasonably good taking the limitations of the theory into account. (author)

Rotational distributions of molecular photoions following resonant excitation

International Nuclear Information System (INIS)

Poliakoff, E.D.; Chan, J.C.K.; White, M.G.

1986-01-01

We demonstrate that the photoelectron energy mediates the rotational energy distribution of N + 2 ions created by photoionization, and conversely, that rotational energy determinations probe resonant excitation in molecular photoionization. Experimentally, this is accomplished by monitoring the dispersed fluorescence from N + 2 (B 2 Σ + /sub u/) photoions to determine their rotational energy distribution. These results demonstrate that while dipole selection rules constrain the total angular momentum of the electron--ion complex, the partitioning of angular momentum between the photoelectron and photoion depends on the photoejection dynamics. Implications for photoionization and electron impact ionizatin studies are discussed

Dynamics of infrared multiphonon dissociation of SF6 by molecular beam method

International Nuclear Information System (INIS)

Grant, E.R.; Coggiola, M.J.; Lee, Y.T.; Schulz, P.A.; Shen, Y.R.

1977-01-01

A crossed molecular beam apparatus has been adapted to study the dynamics of excitation and dissociation of polyatomic molecules in intense IR laser fields. Initial experiments have involved the study of the dissociation of SF 6 by CO 2 laser radiation at 10.6 μm. A molecular beam of SF 6 was formed by supersonic expansion using three stages of differential pumping. A grating tuned pulsed CO 2 TEA laser was used as the excitation source. The laser beam was focused by a 25 cm focal length ZnSe lens, and crossed the molecular beam near its focal point. The fragments produced by multiphonon dissociation of SF 6 within the small interaction region were detected as a function of recoil angle and velocity. (Auth.)

Subarcsecond observations of NGC 7538 IRS 1: Continuum distribution and dynamics of molecular gas

Energy Technology Data Exchange (ETDEWEB)

Zhu, Lei; Shi, Hui [National Astronomical Observatories, Chinese Academy of Sciences, A20 Datun Road, Chaoyang District, Beijing 100012 (China); Zhao, Jun-Hui [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Wright, M. C. H. [Department of Astronomy, University of California, Berkeley, Berkeley, CA 94720 (United States); Sandell, Göran [SOFIA-USRA, NASA Ames Research Center, MS 232-12, Building N232, Rm. 146, P.O. Box 1, Moffett Field, CA 94035-0001 (United States); Wu, Yue-Fang [Department of Astronomy, Peking University, Beijing 100871 (China); Brogan, Crystal; Corder, Stuartt, E-mail: lzhu@nao.cas.cn [NRAO, 520 Edgemont Road, Charlottesville, VA 22903 (United States)

2013-12-10

We report new results based on the analysis of the Submillimeter Array (SMA) and Combined Array for Research in Millimeter-wave Astronomy (CARMA) observations of NGC 7538 IRS 1 at 1.3 and 3.4 mm with subarcsecond resolutions. With angular resolutions ∼0.''7, the SMA and CARMA observations show that the continuum emission at 1.3 and 3.4 mm from the hyper-compact H II region IRS 1 is dominated by a compact source with a tail-like extended structure to the southwest of IRS 1. With a CARMA B-array image at 1.3 mm convolved to 0.''1, we resolve the hyper-compact H II region into two components: an unresolved hyper-compact core, and a north-south extension with linear sizes of <270 AU and ∼2000 AU, respectively. The fine structure observed with CARMA is in good agreement with the previous Very Large Array results at centimeter wavelengths, suggesting that the hyper-compact H II region at the center of IRS 1 is associated with an ionized bipolar outflow. We image the molecular lines OCS(19-18) and CH{sub 3}CN(12-11) as well as {sup 13}CO(2-1) surrounding IRS 1, showing a velocity gradient along the southwest-northeast direction. The spectral line profiles in {sup 13}CO(2-1), CO(2-1), and HCN(1-0) observed toward IRS 1 show broad redshifted absorption, providing evidence for gas infall with rates in the range of 3-10 × 10{sup –3} M {sub ☉} yr{sup –1} inferred from our observations.

Molecular excitation dynamics and relaxation quantum theory and spectroscopy

CERN Document Server

Valkunas, Leonas; Mancal, Tomas

2013-01-01

Meeting the need for a work that brings together quantum theory and spectroscopy to convey excitation processes to advanced students and specialists wishing to conduct research and understand the entire field rather than just single aspects.Written by an experienced author and recognized authority in the field, this text covers numerous applications and offers examples taken from different disciplines. As a result, spectroscopists, molecular physicists, physical chemists, and biophysicists will all find this a must-have for their research. Also suitable as supplementary reading in graduate

Molecular vibrational investigation [FT-IR, FT-Raman, UV-Visible and NMR] on Bis(thiourea) Nickel chloride using HF and DFT calculations.

Science.gov (United States)

Anand, S; Sundararajan, R S; Ramachandraraja, C; Ramalingam, S; Durga, R

2015-03-05

In the present research work, the FT-IR, FT-Raman spectra of the Bis(thiourea) Nickel chloride (BTNC) were recorded and analyzed. The observed fundamental frequencies in finger print and functional group regions were assigned according to their uniqueness region. The computational calculations were carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The present organo-metallic compound was made up of covalent and coordination covalent bonds. The modified vibrational pattern of the complex molecule associated with ligand group was analyzed. Furthermore, the (13)C NMR and (1)H NMR spectral data were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP/6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A investigation on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Excited states

CERN Document Server

Lim, Edward C

1974-01-01

Excited States, Volume I reviews radiationless transitions, phosphorescence microwave double resonance through optical spectra in molecular solids, dipole moments in excited states, luminescence of polar molecules, and the problem of interstate interaction in aromatic carbonyl compounds. The book discusses the molecular electronic radiationless transitions; the double resonance techniques and the relaxation mechanisms involving the lowest triplet state of aromatic compounds; as well as the optical spectra and relaxation in molecular solids. The text also describes dipole moments and polarizab

Communication: IR spectroscopy of neutral transition metal clusters through thermionic emission

NARCIS (Netherlands)

Lapoutre, V. J. F.; Haertelt, M.; Meijer, G.; Fielicke, A.; Bakker, J. M.

2013-01-01

The resonant multiple photon excitation of neutral niobium clusters using tunable infrared (IR) radiation leads to thermionic emission. By measuring the mass-resolved ionization yield as a function of IR wavenumber species selective IR spectra are obtained for Nb-n (n = 5-20) over the 200-350 cm(-1)

Off-resonant vibrational excitation: Orientational dependence and spatial control of photofragments

DEFF Research Database (Denmark)

Machholm, Mette; Henriksen, Niels Engholm

2000-01-01

Off-resonant and resonant vibrational excitation with short intense infrared (IR) laser pulses creates localized oscillating wave packets, but differs by the efficiency of the excitation and surprisingly by the orientational dependence. Orientational selectivity of the vibrational excitation...... of randomly oriented heteronuclear diatomic molecules can be obtained under simultaneous irradiation by a resonant and an off-resonant intense IR laser pulse: Molecules with one initial orientation will be vibrationally excited, while those with the opposite orientation will be at rest. The orientation-dependent...... distribution. (C) 2000 American Institute of Physics....

Fluorescence excitation studies of molecular photoionization in external electric fields

International Nuclear Information System (INIS)

Poliakoff, E.D.; Dehmer, J.L.; Parr, A.C.; Leroi, G.E.

1985-01-01

Using molecular nitrogen as an example, we show that fluorescence excitation spectroscopy can be used to measure partial photoionization cross sections of free molecules in external electric fields. The production of the N 2 + (B 2 Σ/sub u/ + ) state was studied and the threshold for this process was found to shift linearly with the square root of the applied field. This behavior is compared with the hydrogenic case and with previously studied systems

2D IR spectra of cyanide in water investigated by molecular dynamics simulations

Science.gov (United States)

Lee, Myung Won; Carr, Joshua K.; Göllner, Michael; Hamm, Peter; Meuwly, Markus

2013-01-01

Using classical molecular dynamics simulations, the 2D infrared (IR) spectroscopy of CN− solvated in D2O is investigated. Depending on the force field parametrizations, most of which are based on multipolar interactions for the CN− molecule, the frequency-frequency correlation function and observables computed from it differ. Most notably, models based on multipoles for CN− and TIP3P for water yield quantitatively correct results when compared with experiments. Furthermore, the recent finding that T 1 times are sensitive to the van der Waals ranges on the CN− is confirmed in the present study. For the linear IR spectrum, the best model reproduces the full widths at half maximum almost quantitatively (13.0 cm−1 vs. 14.9 cm−1) if the rotational contribution to the linewidth is included. Without the rotational contribution, the lines are too narrow by about a factor of two, which agrees with Raman and IR experiments. The computed and experimental tilt angles (or nodal slopes) α as a function of the 2D IR waiting time compare favorably with the measured ones and the frequency fluctuation correlation function is invariably found to contain three time scales: a sub-ps, 1 ps, and one on the 10-ps time scale. These time scales are discussed in terms of the structural dynamics of the surrounding solvent and it is found that the longest time scale (≈10 ps) most likely corresponds to solvent exchange between the first and second solvation shell, in agreement with interpretations from nuclear magnetic resonance measurements.

Excited-state dynamics of acetylene excited to individual rotational level of the V04K01 subband

Science.gov (United States)

Makarov, Vladimir I.; Kochubei, Sergei A.; Khmelinskii, Igor V.

2006-01-01

Dynamics of the IR emission induced by excitation of the acetylene molecule using the (32Ka0,1,2,ÃAu1←41la1,X˜Σg+1) transition was investigated. The observed IR emission was assigned to transitions between the ground-state vibrational levels. Acetylene fluorescence quenching induced by external electric and magnetic fields acting upon the system prepared using the (34Ka1,ÃAu1←00la0,X˜Σg+1) excitation was also studied. External electric field creates an additional radiationless pathway to the ground-state levels, coupling levels of the ÃAu1 excited state to the quasiresonant levels of the X˜Σg+1 ground state. The level density of the ground state in the vicinity of the excited state is very high, thus the electric-field-induced transition is irreversible, with the rate constant described by the Fermi rule. Magnetic field alters the decay profile without changing the fluorescence quantum yield in collisionless conditions. IR emission from the CCH transient was detected, and was also affected by the external electric and magnetic fields. Acetylene predissociation was demonstrated to proceed by the direct S1→S0 mechanism. The results were explained using the previously developed theoretical approach, yielding values of the relevant model parameters.

Matrix isolation FT-IR spectroscopy and molecular orbital study of sarcosine methyl ester

OpenAIRE

Gómez-Zavaglia, Andrea; Fausto, R.

2004-01-01

N-methylglycine methyl ester (sarcosine-Me) has been studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) and 6-31++G(d,p) basis set, respectively. Twelve different conformers were located in the potential energy surface of the studied compound, with the ASC conformer being the ground conformational state. This form is analogous to the dimethylglycine methyl ester most stable conformer and...

Resonant inelastic X-ray scattering spectra at the Ir L-edge in Na{sub 2}IrO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Igarashi, Jun-ichi, E-mail: junichi.igarashi.kiryu@vc.ibaraki.ac.jp [Faculty of Science, Ibaraki University, Mito, Ibaraki 310-8512 (Japan); Nagao, Tatsuya, E-mail: nagao@gunma-u.ac.jp [Faculty of Engineering, Gunma University, Kiryu, Gunma 376-8515 (Japan)

2016-10-15

Highlights: • A theoretical framework of resonant inelastic X-ray scattering (RIXS) on the basis of the itinerant electron scheme has been developed. • The RIXS theory is applied to iridate Na{sub 2}IrO{sub 3}. • The origins of the multi-peak structure of the excitation spectra found in the RIXS experiment have been assigned to the magnetic and excitonic excitations. - Abstract: We analyze resonant X-ray scattering (RIXS) spectra in Na{sub 2}IrO{sub 3} on the basis of the itinerant electron picture. Employing a multi-orbital tight-binding model on a honeycomb lattice, we find that the zigzag magnetic order is the most stable with sizable energy gap in the one-electron band within the Hartree–Fock approximation. We derive the RIXS spectra, which are connected to the generalized density–density correlation function. We calculate the spectra as a function of excitation energy ω, within the random phase approximation. The spectra consist of the peaks with ω < 20 meV, and of the peaks with 0.4 < ω < 0.8 eV. The former peaks are composed of four bound states in the density–density correlation function, and may be identified as the magnetic excitations, while the latter peaks are composed of 16 bound states below the energy continuum of individual electron–hole pair excitations, and may be identified as the excitonic excitations. The calculated spectra agree qualitatively with the recent RIXS experiment.

Synthesis, geometry optimization, spectroscopic investigations (UV/Vis, excited states, FT-IR) and application of new azomethine dyes

Science.gov (United States)

Shahab, Siyamak; Sheikhi, Masoome; Filippovich, Liudmila; Kumar, Rakesh; Dikusar, Evgenij; Yahyaei, Hooriye; Khaleghian, Mehrnoosh

2017-11-01

In the present work, the quantum theoretical calculations of the molecular structures of the four new synthesized azomethine dyes such as: (E)-N-(4-butoxybenzylidene)-4-((E)-phenyldiazenyl)aniline (PAZB-6), (E)-N-(4-(benzyloxy)benzylidene)-4-((E))-phenyldiazenyl)aniline (PAZB-7), 4-((E)-4-((E)-phenyldiazenyl)phenyl)imino)methyl)phenol (PAZB-8), (E)-N-(4-methoxybenzylidene)-4-((E))-phenyldiazenyl)aniline (PAZB-9) have been predicted using Density Functional Theory in the solvent Dimethylformamide. The geometries of the azomethine dyes were optimized by PBE1PBE/6-31+G* level of theory. The electronic spectra of the title compounds in the solvent DMF was carried out by TDPBE1PBE/6-31+G* method. FT-IR spectra of the title compounds are recorded and discussed. Frontier molecular orbitals, molecular electrostatic potential, electronic properties, natural charges and Natural Bond Orbital (NBO) analysis of the mentioned compounds were investigated and discussed by theoretical calculations. The azomethine dyes were synthesized after quantum chemical modeling for optical applications. A new study of anisotropy of thermal and electrical conductivity of the colored stretched PVA-films have been undertaken.

Excited states rotational effects on the behavior of excited molecules

CERN Document Server

Lim, Edward C

2013-01-01

Excited States, Volume 7 is a collection of papers that discusses the excited states of molecules. The first paper reviews the rotational involvement in intra-molecular in vibrational redistribution. This paper analyzes the vibrational Hamiltonian as to its efficacy in detecting the manifestations of intra-molecular state-mixing in time-resolved and time-averaged spectroscopic measurements. The next paper examines the temporal behavior of intra-molecular vibration-rotation energy transfer (IVRET) and the effects of IVRET on collision, reaction, and the decomposition processes. This paper also

Theory of Excitation Transfer between Two-Dimensional Semiconductor and Molecular Layers

Science.gov (United States)

Specht, Judith F.; Verdenhalven, Eike; Bieniek, Björn; Rinke, Patrick; Knorr, Andreas; Richter, Marten

2018-04-01

The geometry-dependent energy transfer rate from an electrically pumped inorganic semiconductor quantum well into an organic molecular layer is studied theoretically. We focus on Förster-type nonradiative excitation transfer between the organic and inorganic layers and include quasimomentum conservation and intermolecular coupling between the molecules in the organic film. (Transition) partial charges calculated from density-functional theory are used to calculate the coupling elements. The partial charges describe the spatial charge distribution and go beyond the common dipole-dipole interaction. We find that the transfer rates are highly sensitive to variations in the geometry of the hybrid inorganic-organic system. For instance, the transfer efficiency is improved by up to 2 orders of magnitude by tuning the spatial arrangement of the molecules on the surface: Parameters of importance are the molecular packing density along the effective molecular dipole axis and the distance between the molecules and the surface. We also observe that the device performance strongly depends on the orientation of the molecular dipole moments relative to the substrate dipole moments determined by the inorganic crystal structure. Moreover, the operating regime is identified where inscattering dominates over unwanted backscattering from the molecular layer into the substrate.

Vibrational excitations in molecular layers probed by ballistic electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Kajen, Rasanayagam Sivasayan; Chandrasekhar, Natarajan [Institute of Materials Research and Engineering, 3 Research Link, 117602 (Singapore); Feng Xinliang; Muellen, Klaus [Max-Planck-Institut fuer Polymerforschung, Postfach 3148, D-55021 Mainz (Germany); Su Haibin, E-mail: n-chandra@imre.a-star.edu.sg, E-mail: muellen@mpip-mainz.mpg.de, E-mail: hbsu@ntu.edu.sg [Division of Materials Science, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore)

2011-10-28

We demonstrate the information on molecular vibrational modes via the second derivative (d{sup 2}I{sub B}/dV{sup 2}) of the ballistic electron emission spectroscopy (BEES) current. The proposed method does not create huge fields as in the case of conventional derivative spectroscopy and maintains a zero bias across the device. BEES studies carried out on three different types of large polycyclic aromatic hydrocarbon (PAH) molecular layers show that the d{sup 2}I{sub B}/dV{sup 2} spectra consist of uniformly spaced peaks corresponding to vibronic excitations. The peak spacing is found to be identical for molecules within the same PAH family though the BEES onset voltage varies for different molecules. In addition, injection into a particular orbital appears to correspond to a specific vibrational mode as the manifestation of the symmetry principle.

Reduction of the Glauber amplitude for electron impact rotational excitation of quadrupolar molecular ions

International Nuclear Information System (INIS)

Mathur, K.C.; Gupta, G.P.; Pundir, R.S.

1981-06-01

A reduction of the Glauber amplitude for the rotational excitation of pure quadrupolar molecular ions by electron impact is presented in a form suitable for numerical evaluation. The differential cross-section is expressed in terms of one dimensional integrals over impact parameter. (author)

UV/IR Filaments for High Resolution Novel Spectroscopic Interrogation of Plumes on Nuclear Materials

Science.gov (United States)

2016-06-01

Raman spectroscopy of plumes created by a laser filament. The molecules to be detected are excited by the short pulse IR pulse, while the co-propagating... spectroscopy of gas samples has been demonstrated in IR filaments [32], using the fs pulse of the filament (800 nm) to vibrationally excite the components...Petit. Isotope ratio determination of uranium by optical emission spectroscopy on a laser -produced plasma; basic investigation and analytical results

Simulations of the dissociation of small helium clusters with ab initio molecular dynamics in electronically excited states

International Nuclear Information System (INIS)

Closser, Kristina D.; Head-Gordon, Martin; Gessner, Oliver

2014-01-01

The dynamics resulting from electronic excitations of helium clusters were explored using ab initio molecular dynamics. The simulations were performed with configuration interaction singles and adiabatic classical dynamics coupled to a state-following algorithm. 100 different configurations of He 7 were excited into the 2s and 2p manifold for a total of 2800 trajectories. While the most common outcome (90%) was complete fragmentation to 6 ground state atoms and 1 excited state atom, 3% of trajectories yielded bound, He 2 * , and <0.5% yielded an excited helium trimer. The nature of the dynamics, kinetic energy release, and connections to experiments are discussed

Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation

Science.gov (United States)

Delor, Milan; Archer, Stuart A.; Keane, Theo; Meijer, Anthony J. H. M.; Sazanovich, Igor V.; Greetham, Gregory M.; Towrie, Michael; Weinstein, Julia A.

2017-11-01

Ultrafast electron transfer in condensed-phase molecular systems is often strongly coupled to intramolecular vibrations that can promote, suppress and direct electronic processes. Recent experiments exploring this phenomenon proved that light-induced electron transfer can be strongly modulated by vibrational excitation, suggesting a new avenue for active control over molecular function. Here, we achieve the first example of such explicit vibrational control through judicious design of a Pt(II)-acetylide charge-transfer donor-bridge-acceptor-bridge-donor 'fork' system: asymmetric 13C isotopic labelling of one of the two -C≡C- bridges makes the two parallel and otherwise identical donor→acceptor electron-transfer pathways structurally distinct, enabling independent vibrational perturbation of either. Applying an ultrafast UVpump(excitation)-IRpump(perturbation)-IRprobe(monitoring) pulse sequence, we show that the pathway that is vibrationally perturbed during UV-induced electron transfer is dramatically slowed down compared to its unperturbed counterpart. One can thus choose the dominant electron transfer pathway. The findings deliver a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.

Fluorescent molecular probes based on excited state prototropism in lipid bilayer membrane

Science.gov (United States)

Mohapatra, Monalisa; Mishra, Ashok K.

2012-03-01

Excited state prototropism (ESPT) is observed in molecules having one or more ionizable protons, whose proton transfer efficiency is different in ground and excited states. The interaction of various ESPT molecules like naphthols and intramolecular ESPT (ESIPT) molecules like hydroxyflavones etc. with different microheterogeneous media have been studied in detail and excited state prototropism as a probe concept has been gaining ground. The fluorescence of different prototropic forms of such molecules, on partitioning to an organized medium like lipid bilayer membrane, often show sensitive response to the local environment with respect to the local structure, physical properties and dynamics. Our recent work using 1-naphthol as an ESPT fluorescent molecular probe has shown that the incorporation of monomeric bile salt molecules into lipid bilayer membranes composed from dipalmitoylphosphatidylcholine (DPPC, a lung surfactant) and dimyristoylphosphatidylcholine (DMPC), in solid gel and liquid crystalline phases, induce appreciable wetting of the bilayer up to the hydrocarbon core region, even at very low (fisetin, an ESIPT molecule having antioxidant properties, in lipid bilayer membrane has been sensitively monitored from its intrinsic fluorescence behaviour.

Combinatorial screening of halide perovskite thin films and solar cells by mask-defined IR laser molecular beam epitaxy

OpenAIRE

Kawashima, Kazuhiro; Okamoto, Yuji; Annayev, Orazmuhammet; Toyokura, Nobuo; Takahashi, Ryota; Lippmaa, Mikk; Itaka, Kenji; Suzuki, Yoshikazu; Matsuki, Nobuyuki; Koinuma, Hideomi

2017-01-01

Abstract As an extension of combinatorial molecular layer epitaxy via ablation of perovskite oxides by a pulsed excimer laser, we have developed a laser molecular beam epitaxy (MBE) system for parallel integration of nano-scaled thin films of organic?inorganic hybrid materials. A pulsed infrared (IR) semiconductor laser was adopted for thermal evaporation of organic halide (A-site: CH3NH3I) and inorganic halide (B-site: PbI2) powder targets to deposit repeated A/B bilayer films where the thic...

Bibliography of atomic and molecular excitation in heavy particle collisions, 1950--1975

International Nuclear Information System (INIS)

Hawthorne, S.W.; Thomas, E.W.; Barnett, C.F.; Crandall, D.H.; Gilbody, H.B.; Kirkpatrick, M.I.; McDaniel, E.W.; Phaneuf, R.A.

1979-02-01

This annotated bibliography lists published work on atomic and molecular excitation in heavy particle collisions for the period 1950 to 1975. Sources include scientific journals, abstract compilations, conference proceedings, books, and reports. The bibliography is arranged alphabetically by author. Each entry indicates whether the work was experimental or theoretical, what energy range was covered, and what reactants were investigated. Following the bibliographical listing are indexes of reactions and authors

Photoionization dynamics of excited molecular states

International Nuclear Information System (INIS)

Dehmer, J.L.; O'Halloran, M.A.; Tomkins, F.S.; Dehmer, P.M.; Pratt, S.T.

1987-01-01

Resonance Enhanced Multiphoton Ionization (REMPI) utilizes tunable dye lasers to ionize an atom or molecule by first preparing an excited state by multiphoton absorption and then ionizing that state before it can decay. This process is highly selective with respect to both the initial and resonant intermediate states of the target, and it can be extremely sensitive. In addition, the products of the REMPI process can be detected as needed by analyzing the resulting electrons, ions, fluorescence, or by additional REMPI. This points to a number of opportunities for exploring excited state physics and chemistry at the quantum-state-specific level. Here we will first give a brief overview of the large variety of experimental approaches to excited state phenomena made possible by REMPI. Then we will examine in more detail, recent studies of the three photon resonant, four photon (3 + 1) ionization of H 2 via the C 'PI/sup u/ state. Strong non-Franck-Condon behavior in the photoelectron spectra of this nominally simple Rydberg state has led to the examination of a variety of dynamical mechanisms. Of these, the role of doubly excited autoionizing states now seems decisive. Progress on photoelectron studies of autoionizing states in H 2 , excited in a (2 + 1) REMPI process via the E, F 1 Σ/sub g/ + will also be briefly discussed. 26 refs., 7 figs

High-molecular weight adiponectin/HOMA-IR ratio as a biomarker of metabolic syndrome in urban multiethnic Brazilian subjects.

Science.gov (United States)

de Abreu, Virgínia Genelhu; Martins, Cyro José de Moraes; de Oliveira, Patricia Aguiar Cardoso; Francischetti, Emilio Antonio

2017-01-01

Metabolic syndrome (MetS) has an important epidemiological relevance due to its increasing prevalence and association with type 2 diabetes and cardiovascular disease. Insulin resistance is a core feature of the MetS. HOMA-IR is a robust clinical and epidemiological marker of MetS. Adiponectin is an adipokine with insulin-sensitizing and anti-inflammatory functions; its levels decrease as number of components of MetS increases. High-molecular weight adiponectin (HMWA) is the multimer responsible for the relationship of adiponectin with insulin sensitivity. HOMA-IR and HMWA are suitable candidates for MetS biomarkers. The ratio of adiponectin to HOMA-IR has been validated as a powerful index of MetS and considered a better marker of its presence, than either HOMA-IR or adiponectin alone, in selected homogeneous populations. We compared the strength of association between HMWA, HOMA-IR and HMWA/HOMA-IR ratio with MetS and its key components. Our data have shown that the median (25th, 75th percentile) of HMWA/HOMA-IR ratio was lower in subjects with MetS [0.51 (0.33, 1.31)] as compared to those without it [2.19 (1.13, 4.71)]. The correlation coefficient (r) was significantly higher for HMWA/HOMA-IR ratio as compared to HMWA for waist circumference (-0.65; -0.40, respectively); mean blood pressure (-0.27; -0.14, respectively); fasting glucose (-0.38; -0.19, respectively); HDL-cholesterol (0.44; 0.40, respectively); and triglycerides (-0.35; -0.18, respectively). In a multivariable logistic regression analysis, the HMWA/HOMA-IR ratio was a sensitive predictor for MetS, being the only marker that was significantly associated with each and all the individual components of the syndrome. These results expand on previous studies in that we used the active circulating form of adiponectin, i.e. HMWA, and represent a typical Brazilian cohort characterized by intense interethnic admixture. Thus, the HMWA/HOMA-IR ratio is a minimally invasive biomarker for MetS that could be

Cationic polyhydrido cluster complexes. Crystal and molecular structures of (Ir3(Ph2P(CH2)3PPh2)3(H)7(CO))2+ and (Ir3(Ph2P(CH2)2(2-py))3(H)7)2+

International Nuclear Information System (INIS)

Hsienhau Wang; Casalnuovo, A.L.; Johnson, B.J.; Mueting, A.M.; Pignolet, L.H.

1988-01-01

Two new cationic polyhydrido cluster complexes of iridium have been synthesized and characterized by single-crystal x-ray diffraction and by ir and 1 H and 31 P NMR spectroscopy (Ir 3 (dppp) 3 (H) 7 (CO)) 2+ (2) and (Ir3 (PN) 3 (H) 7)2+ (5), where dppp = 1,3-bis(diphenylphosphino)propane and PN = 1-(2-pyridyl)-2-(diphenylphosphino)ethane, were synthesized by the reaction of CO with (Ir 3 (dppp) 3 (H) 7 ) 2+ (1) in CH 2 Cl 2 solution and H 2 with (Ir(PN)(COD)) + (4) in CH 3 OH solution, respectively. Crystal structures for both compounds is reported. The hydride positions were not located in the crystal structure analyses but were deduced from structural and 1 H NMR data. The molecular structure of 2 consists of a bilateral triangle of three iridium atoms with a carbonyl at the vertex and a chelating dppp ligand on each iridium atom. 1 H NMR data with use of acetone-d 6 as solvent showed that 2 possesses four doubly bridging hydrides and three terminal hydrides, yielding C 1 symmetry. The molecular structure of 5 consists of an approximately equilateral triangle of three iridium atoms (average Ir-Ir distance 2.746 (1) angstrom) with one PN ligand chelated to each iridium atom. 1 H NMR analysis, with use of CD 2 Cl 2 as solvent, showed that 5 has one triply bridging hydride and six terminal hydrides, giving C 3 symmetry. (Ir 3 (dppp) 3 (H) 7 (CH 3 C 6 H 4 NC)) 2+ (3) a complex structurally analogous to 2, was synthesized from 1 and p-tolyl isocyanide in CH 2 Cl 2 solution and characterized by ir and 1 H and 31 P NMR spectroscopy. 44 refs., 3 figs., 3 tabs

Dynamical coupling of plasmons and molecular excitations by hybrid quantum/classical calculations: time-domain approach

International Nuclear Information System (INIS)

Sakko, Arto; Rossi, Tuomas P; Nieminen, Risto M

2014-01-01

The presence of plasmonic material influences the optical properties of nearby molecules in untrivial ways due to the dynamical plasmon-molecule coupling. We combine quantum and classical calculation schemes to study this phenomenon in a hybrid system that consists of a Na 2 molecule located in the gap between two Au/Ag nanoparticles. The molecule is treated quantum-mechanically with time-dependent density-functional theory, and the nanoparticles with quasistatic classical electrodynamics. The nanoparticle dimer has a plasmon resonance in the visible part of the electromagnetic spectrum, and the Na 2 molecule has an electron-hole excitation in the same energy range. Due to the dynamical interaction of the two subsystems the plasmon and the molecular excitations couple, creating a hybridized molecular-plasmon excited state. This state has unique properties that yield e.g. enhanced photoabsorption compared to the freestanding Na 2 molecule. The computational approach used enables decoupling of the mutual plasmon-molecule interaction, and our analysis verifies that it is not legitimate to neglect the backcoupling effect when describing the dynamical interaction between plasmonic material and nearby molecules. Time-resolved analysis shows nearly instantaneous formation of the coupled state, and provides an intuitive picture of the underlying physics. (paper)

Fission fragment excited laser system

Science.gov (United States)

McArthur, David A.; Tollefsrud, Philip B.

1976-01-01

A laser system and method for exciting lasing action in a molecular gas lasing medium which includes cooling the lasing medium to a temperature below about 150 K and injecting fission fragments through the lasing medium so as to preferentially excite low lying vibrational levels of the medium and to cause population inversions therein. The cooled gas lasing medium should have a mass areal density of about 5 .times. 10.sup.-.sup.3 grams/square centimeter, relaxation times of greater than 50 microseconds, and a broad range of excitable vibrational levels which are excitable by molecular collisions.

Two-dimensional infrared spectroscopy of vibrational polaritons.

Science.gov (United States)

Xiang, Bo; Ribeiro, Raphael F; Dunkelberger, Adam D; Wang, Jiaxi; Li, Yingmin; Simpkins, Blake S; Owrutsky, Jeffrey C; Yuen-Zhou, Joel; Xiong, Wei

2018-04-19

We report experimental 2D infrared (2D IR) spectra of coherent light-matter excitations--molecular vibrational polaritons. The application of advanced 2D IR spectroscopy to vibrational polaritons challenges and advances our understanding in both fields. First, the 2D IR spectra of polaritons differ drastically from free uncoupled excitations and a new interpretation is needed. Second, 2D IR uniquely resolves excitation of hybrid light-matter polaritons and unexpected dark states in a state-selective manner, revealing otherwise hidden interactions between them. Moreover, 2D IR signals highlight the impact of molecular anharmonicities which are applicable to virtually all molecular systems. A quantum-mechanical model is developed which incorporates both nuclear and electrical anharmonicities and provides the basis for interpreting this class of 2D IR spectra. This work lays the foundation for investigating phenomena of nonlinear photonics and chemistry of molecular vibrational polaritons which cannot be probed with traditional linear spectroscopy.

Molecular Excitation Energies from Time-Dependent Density Functional Theory Employing Random-Phase Approximation Hessians with Exact Exchange.

Science.gov (United States)

Heßelmann, Andreas

2015-04-14

Molecular excitation energies have been calculated with time-dependent density-functional theory (TDDFT) using random-phase approximation Hessians augmented with exact exchange contributions in various orders. It has been observed that this approach yields fairly accurate local valence excitations if combined with accurate asymptotically corrected exchange-correlation potentials used in the ground-state Kohn-Sham calculations. The inclusion of long-range particle-particle with hole-hole interactions in the kernel leads to errors of 0.14 eV only for the lowest excitations of a selection of three alkene, three carbonyl, and five azabenzene molecules, thus surpassing the accuracy of a number of common TDDFT and even some wave function correlation methods. In the case of long-range charge-transfer excitations, the method typically underestimates accurate reference excitation energies by 8% on average, which is better than with standard hybrid-GGA functionals but worse compared to range-separated functional approximations.

Approximate inclusion of triple excitations in combined coupled cluster/molecular mechanics: Calculations of electronic excitation energies in solution for acrolein, water, formamide, and n-methylacetamide

DEFF Research Database (Denmark)

Sneskov, Kristian; Gras, Eduard Matito; Kongsted, Jacob

2010-01-01

as being applicable for averaging over many solvent configurations derived from, for example, molecular simulations. We test the proposed model using as a benchmark the two lowest-lying valence singlet excitations (n → π* and π → π*) of acrolein, formamide, and N-methylacetamide in aqueous solution as well...

Single photon infrared emission spectroscopy: a study of IR emission from UV laser excited PAHs between 3 and 15 micrometers

Science.gov (United States)

Cook, D. J.; Schlemmer, S.; Balucani, N.; Wagner, D. R.; Harrison, J. A.; Steiner, B.; Saykally, R. J.

1998-01-01

Single-photon infrared emission spectroscopy (SPIRES) has been used to measure emission spectra from polycyclic aromatic hydrocarbons (PAHs). A supersonic free-jet expansion has been used to provide emission spectra of rotationally cold and vibrationally excited naphthalene and benzene. Under these conditions, the observed width of the 3.3-micrometers (C-H stretch) band resembles the bandwidths observed in experiments in which emission is observed from naphthalene with higher rotational energy. To obtain complete coverage of IR wavelengths relevant to the unidentified infrared bands (UIRs), UV laser-induced desorption was used to generate gas-phase highly excited PAHs. Lorentzian band shapes were convoluted with the monochromator-slit function in order to determine the widths of PAH emission bands under astrophysically relevant conditions. Bandwidths were also extracted from bands consisting of multiple normal modes blended together. These parameters are grouped according to the functional groups mostly involved in the vibration, and mean bandwidths are obtained. These bandwidths are larger than the widths of the corresponding UIR bands. However, when the comparison is limited to the largest PAHs studied, the bandwidths are slightly smaller than the corresponding UIR bands. These parameters can be used to model emission spectra from PAH cations and cations of larger PAHs, which are better candidate carriers of the UIRs.

Molecular structure, vibrational analysis (IR and Raman) and quantum chemical investigations of 1-aminoisoquinoline

Science.gov (United States)

Sivaprakash, S.; Prakash, S.; Mohan, S.; Jose, Sujin P.

2017-12-01

Quantum chemical calculations of energy and geometrical parameters of 1-aminoisoquinoline [1-AIQ] were carried out by using DFT/B3LYP method using 6-311G (d,p), 6-311G++(d,p) and cc-pVTZ basis sets. The vibrational wavenumbers were computed for the energetically most stable, optimized geometry. The vibrational assignments were performed on the basis of potential energy distribution (PED) using VEDA program. The NBO analysis was done to investigate the intra molecular charge transfer of the molecule. The frontier molecular orbital (FMO) analysis was carried out and the chemical reactivity descriptors of the molecule were studied. The Mulliken charge analysis, molecular electrostatic potential (MEP), HOMO-LUMO energy gap and the related properties were also investigated at B3LYP level. The absorption spectrum of the molecule was studied from UV-Visible analysis by using time-dependent density functional theory (TD-DFT). Fourier Transform Infrared spectrum (FT-IR) and Raman spectrum of 1-AIQ compound were analyzed and recorded in the range 4000-400 cm-1 and 3500-100 cm-1 respectively. The experimentally determined wavenumbers were compared with those calculated theoretically and they complement each other.

A “Swingable” straight-chain affinity molecule immobilized on a semi-conductor electrode for photo-excited current-based molecular sensing

International Nuclear Information System (INIS)

Takatsuji, Yoshiyuki; Wakabayashi, Ryo; Sakakura, Tatsuya; Haruyama, Tetsuya

2015-01-01

The molecular affinities of biomolecules have found applications in the areas of clinical diagnostics, drug discovery, as well as allied fields of study. An affinity sensor is a unique in situ assay tool, which is valuable and convenient in practical situations. In this study, we designed a photo-excitable molecular interface with an affinity domain and fabricated with a “swingable” straight-chain affinity molecule immobilized on a semi-conductor electrode (SCE). The straight-chain affinity molecule possessed a photo-excitable dye at one end and was bound to the SCE surface at the other by the EC tag method, which was developed previously. A straight-chain molecule is too long to transfer electrons from the photo-excited dye to the conduction band of the SCE. However, the straight-chain molecule was designed with a “swing” structure, which made the transfer of electrons possible. The central region of the chain molecule has an affinity to the activated estrogen receptor (ER). When the activated ER bound to the affinity region, the molecular lost its swingable function, the electron transfer from the photo-excited dye to the SCE was consequently suppressed. Based on the unique swingable molecular interface, the affinity sensor can be used to determine the in situ concentration of endocrine disrupter ESTROGEN (17β-estradiol) at concentrations ranging from 2 to 10 nM with very good reproducibility. The superior assay reproducibility is responsible for the success of the EC tag method, which is a quantitative method for immobilizing molecules on SCE.

Single photon excimer laser photodissociation of highly vibrationally excited polyatomic molecules

International Nuclear Information System (INIS)

Tiee, J.J.; Wampler, F.B.; Rice, W.W.

1980-01-01

The ir + uv photodissociation of SF 6 has been performed using CO 2 and ArF lasers. The two-color photolysis significantly enhances the photodissociation process over ArF irradiation alone and is found to preserve the initial isotopic specificity of the ir excitation process

Excited states 2

CERN Document Server

Lim, Edward C

2013-01-01

Excited States, Volume 2 is a collection of papers that deals with molecules in the excited states. The book describes the geometries of molecules in the excited electronic states. One paper describes the geometries of a diatomic molecule and of polyatomic molecules; it also discusses the determination of the many excited state geometries of molecules with two, three, or four atoms by techniques similar to diatomic spectroscopy. Another paper introduces an ordered theory related to excitons in pure and mixed molecular crystals. This paper also presents some experimental data such as those invo

Infrared (1-12 μm) atomic and molecular emission signatures from energetic materials using laser-induced breakdown spectroscopy

Science.gov (United States)

Kumi Barimah, E.; Hömmerich, U.; Brown, E.; Yang, C. S.-C.; Trivedi, S. B.; Jin, F.; Wijewarnasuriya, P. S.; Samuels, A. C.; Snyder, A. P.

2013-05-01

Laser-induced breakdown spectroscopy (LIBS) is a powerful analytical technique to detect the elemental composition of solids, liquids, and gases in real time. For example, recent advances in UV-VIS LIBS have shown great promise for applications in chemical, biological, and explosive sensing. The extension of conventional UVVIS LIBS to the near-IR (NIR), mid-IR (MIR) and long wave infrared (LWIR) regions (~1-12 μm) offers the potential to provide additional information due to IR atomic and molecular signatures. In this work, a Q-switched Nd: YAG laser operating at 1064 nm was employed as the excitation source and focused onto several chlorate and nitrate compounds including KClO3, NaClO3, KNO3, and NaNO3 to produce intense plasma at the target surface. IR LIBS studies on background air, KCl , and NaCl were also included for comparison. All potassium and sodium containing samples revealed narrow-band, atomic-like emissions assigned to transitions of neutral alkali-metal atoms in accordance with the NIST atomic spectra database. In addition, first evidence of broad-band molecular LIBS signatures from chlorate and nitrate compounds were observed at ~10 μm and ~7.3 μm, respectively. The observed molecular emissions showed strong correlation with FTIR absorption spectra of the investigated materials.

Conformational study of sarcosine as probed by matrix-isolation FT-IR spectroscopy and molecular orbital calculations

OpenAIRE

Gómez-Zavaglia, Andrea; Fausto, R.

2003-01-01

Sarcosine (N-methylglycine) has been studied by matrix-isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d, p) and 6-31++G(d, p) basis set, respectively. Eleven different conformers were located in the potential energy surface (PES) of sarcosine, with the ASC conformer being the ground conformational state. This form is analogous to the glycine most stable conformer and is characterized by a NH...O= intramole...

Infrared multiphoton dissociation of acrolein. Time-resolved observation of CO ( v = 1) IR emission at 4.7 μm

Science.gov (United States)

Chowdhury, P. K.; Rama Rao, K. V. S.; Mittal, J. P.

1994-02-01

In contrast to the photochemistry of electronically excited acrolein producing vinyl and formyl radicals via CC bond rupture, multiphoton vibrationally excited molecules undergo concerted dissociation generating CO and ethylene. Vibrational excitation in the CO product is detected immediately following the CO 2 laser pulse by observing IR emission at 4.7 μm. The decay of the IR emission was studied as a function of acrolein pressure. A vibrational-vibrational relaxation rate constant of CO ( v=1) by acrolein is found to be 1240 ± 200 Torr -1 s -1.

Competing reaction channels in IR-laser-induced unimolecular reactions

International Nuclear Information System (INIS)

Berman, M.R.

1981-01-01

The competing reaction channels in the unimolecular decomposition of two molecules, formaldehyde and tetralin were studied. A TEA CO 2 laser was used as the excitation source in all experiments. The dissociation of D 2 CO was studied by infrared multiphoton dissociation (MPD) and the small-molecule nature of formaldehyde with regard to MPD was explored. The effect of collisions in MPD were probed by the pressure dependence of the MPD yield and ir fluorescence from multiphoton excited D 2 CO. MPD yield shows a near cubic dependence in pure D 2 CO which is reduced to a 1.7 power dependence when 15 torr of NO is added. The peak amplitude of 5 μm ir fluorescence from D 2 CO is proportional to the square of the D 2 CO pressure in pure D 2 CO or in the presence of 50 torr of Ar. Results are explained in terms of bottlenecks to excitation at the v = 1 level which are overcome by a combination of vibrational energy transfer and rotational relaxation. The radical/molecule branching ratio in D 2 CO MPD was 0.10 +- 0.02 at a fluence of 125 J/cm 2 at 946.0 cm -1 . The barrier height to molecular dissociation was calculated to be 3.6 +- 2.0 kcal/mole below the radical threshold or 85.0 +- 3.0 kcal/mole above the ground state of D 2 CO. In H 2 CO, this corresponds to 2.5 +- 2.0 kcal/mole below the radical threshold or 83.8 +- 3.0 kcal/mole above the ground state. Comparison with uv data indicate that RRKM theory is an acceptable description of formaldehyde dissociation in the 5 to 10 torr pressure range. The unimolecular decomposition of tetralin was studied by MPD and SiF 4 - sensitized pyrolysis. Both techniques induce decomposition without the interference of catalytic surfaces. Ethylene loss is identified as the lowest energy reaction channel. Dehydrogenation is found to result from step-wise H atom loss. Isomerization via disproportionation is also identified as a primary reaction channel

Equations describing coherent and partially coherent multilevel molecular excitation induced by pulsed Raman transitions: III

International Nuclear Information System (INIS)

Shore, B.W.; Sacks, R.; Karr, T.

1987-01-01

This memo discusses the equations of motion used to describe multilevel molecular excitation induced by Raman transitions. These equations are based upon the time-dependent Schroedinger equation expressed in a basis of molecular energy states. A partition of these states is made into two sets, those that are far from resonance (and hence unpopulated) and those that are close to resonance, either by one-photon transition or two-photon (Raman) processes. By adiabatic elimination an effective Schroedinger equation is obtained for the resonance states alone. The effective Hamiltonian is expressible in terms of a polarizibility operator

NEAR-IR TWO PHOTON MICROSCOPY IMAGING OF SILICA NANOPARTICLES FUNCTIONALIZED WITH ISOLATED SENSITIZED Yb(III) CENTERS

Energy Technology Data Exchange (ETDEWEB)

Lapadula, Giuseppe; Bourdolle, Adrien; Allouche, Florian; Conley, Matthew P.; Maron, Laurent; Lukens, Wayne W.; Guyot, Yannick; Andraud, Chantal; Brasselet, Sophie; Copé; ret, Christophe; Maury, Olivier; Andersen, Richard A.

2013-01-12

Bright nano objects emitting in the near infrared with a maximal cross section of 41.4 x 103 GM (Goppert Mayer), were prepared by implanting ca. 180 4,4 diethylaminostyryl 2,2 bipyridine (DEAS) Yb(III) complexes on the surface of 12 nm silica nanoparticles. The surface complexes ([DEAS Ln SiO2], Ln =Y,Yb) were characterized using IR, solid state NMR, UV Vis, EXAFS spectroscopies in combination with the preparation and characterization of similar molecular analogues by analytical techniques (IR, solution NMR, UV Vis, X ray crystallography) as well as DFT calculations. Starting from the partial dehydroxylation of the silica at 700 C on high vacuum having 0.8 OH.nm 2, the grafting of Ln(N(SiMe3)2)3 generate ≤SiO Ln(N(SiMe3)2)2, which upon thermal step and coordination of the DEAS chromophore yields (≤SiO)3Ln(DEAS). Surface and molecular analogues display similar properties, in terms of DEAS binding constants absorption maxima and luminescence properties (intense emission band assigned to a ligand centered CT fluorescence and life time) in the solid state, consistent with the molecular nature of the surface species. The densely functionalized nanoparticles can be dispersed via ultra-sonication in small ca. 15-20 nm aggregates (1 to 6 elementary particles) that were detected using two photon microscopy imaging at 720 nm excitation, making them promising nano objects for bio imaging.

Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

NARCIS (Netherlands)

Keller, D.E.; Visser, T.; Soulimani, F.; Koningsberger, D.C.; Weckhuysen, B.M.

2007-01-01

The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups,

Spectroscopic (FT-IR, FT-Raman, NMR and UV-Visible) and quantum chemical studies of molecular geometry, Frontier molecular orbital, NLO, NBO and thermodynamic properties of salicylic acid.

Science.gov (United States)

Suresh, S; Gunasekaran, S; Srinivasan, S

2014-11-11

The solid phase FT-IR and FT-Raman spectra of 2-hydroxybenzoic acid (salicylic acid) have been recorded in the region 4000-400 and 4000-100 cm(-1) respectively. The optimized molecular geometry and fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method and a comparative study between Hartree Fork (HF) method at 6-311++G(d,p) level basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimentally obtained FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated potential energy distribution (PED). The time dependent DFT method is employed to predict its absorption energy and oscillator strength. The linear polarizability (α) and the first order hyper polarizability (β) values of the investigated molecule have been computed. The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MEP) are also performed. Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Published by Elsevier B.V.

FT-IR, FT-Raman, and DFT computational studies of melaminium nitrate molecular-ionic crystal

Science.gov (United States)

Tanak, Hasan; Marchewka, Mariusz K.

2013-02-01

The experimental and theoretical vibrational spectra of melaminium nitrate were studied. The Raman and infrared (FT-IR) spectra of the melaminium nitrate and its deuterated analogue were recorded in the solid phase. Molecular geometry and vibrational frequency values of melaminium nitrate in the electronic ground state were calculated using the density functional method (B3LYP) with the 6-31++G(d,p) basis set. The calculated results show that the optimized geometry can well reproduce the crystal structure, and the theoretical vibrational frequency values show good agreement with experimental values. The NBO analysis reveals that the N-H···O and N-H···N intermolecular interactions significantly influence crystal packing in this molecule.

Effects of rust in the crack face on crack detection based on Sonic-IR method

International Nuclear Information System (INIS)

Harai, Y.; Izumi, Y.; Tanabe, H.; Takamatsu, T.; Sakagami, T.

2015-01-01

Sonic-IR, which is based on the thermographic detection of the temperature rise due to frictional heating at the defect faces under ultrasonic excitation, has an advantage in the detection of closed and small defects. However, this method has a lot of nuclear factors relating to heat generation. In this study, effects of rust in the crack faces on the crack detection based on the sonic-IR method is experimentally investigated by using crack specimens. The heat generation by ultrasonic excitation was observed regularly during rust accelerated test using original device. The distribution of temperature change around the crack was changed with the progress of rust. This change in heat generation, it believed to be due to change in the contact state of the crack surface due to rust. As a result, it was found that heat generation by ultrasonic excitation is affected by rust in the crack faces. And it was also found that crack detection can be conducted by sonic-IR even if rust was generated in the crack faces. (author)

Spectroscopic investigations (FT-IR & FT-Raman) and molecular docking analysis of 6-[1-methyl-4-nitro-1H-imidazol-5-yl) sulfonyl]-7H-purine

Science.gov (United States)

Prasath, M.; Govindammal, M.; Sathya, B.

2017-10-01

The Azathioprine is used as anticancer agent. Azathioprine is chemically called 6-[1-methyl-4-nitro-1H-imidazol-5-yl) sulfonyl]-7H-purine (6M4N5P). The vibrational analysis of the 6M4N5P compound was carried out by using FT-IR and FT-Raman spectroscopic techniques and compared with aspects. The optimized geometry, frequency and intensity of the vibrational bands of 6M4N5P were obtained from the HF and DFT methods with 6-31G (d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FT-IR and FT-Raman spectra. The calculated Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) energies show that charge transfer occur within the molecule. MEP (Molecular Electrostatic Potential) is very useful in the investigation of the charge distributions and molecular structure. The molecule orbital contributions were determined by using the total density of states (TDOS). A molecular docking analysis has been carried out to understand the conformational change and electrostatic properties of 6M4N5P in the active site of Rac1-Receptor.

Vibrational spectra (FT-IR, FT-Raman), frontier molecular orbital, first hyperpolarizability, NBO analysis and thermodynamics properties of Piroxicam by HF and DFT methods

Science.gov (United States)

Suresh, S.; Gunasekaran, S.; Srinivasan, S.

2015-03-01

The solid phase FT-IR and FT-Raman spectra of 4-Hydroxy-2-methyl-N-(2-pyridinyl)-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide (Piroxicam) have been recorded in the region 4000-400 and 4000-100 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of piroxicam in the ground state have been calculated by Hartree-Fock (HF) and density functional theory (DFT) methods using 6-311++G(d,p) basis set. The calculated harmonic vibrational frequencies are scaled and they are compared with experimental obtained by FT-IR and FT-Raman spectra. A detailed interpretation of the vibrational spectra of the title compound has been made on the basis of the calculated potential energy distribution (PED). The electronic properties, such as HOMO and LUMO energies, molecular electrostatic potential (MESP) are also performed. The linear polarizability (α) and the first order hyper polarizability (β) values of the title compound have been computed. The molecular stability arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis.

Measurement of IR optics with linear coupling's action-angle parametrization

Science.gov (United States)

Luo, Y.; Bai, M.; Pilat, F.; Satogata, T.; Trbojevic, D.

2005-08-01

Linear coupling’s action-angle parametrization is convenient for interpretation of turn-by-turn beam position monitor (BPM) data. We demonstrate how to apply this parametrization to extract Twiss and coupling parameters in interaction regions (IRs), using BPMs on each side of a long IR drift region. Example data were acquired at the Relativistic Heavy Ion Collider, using an ac dipole to excite a single transverse eigenmode. We have measured the waist of the β function and its Twiss and coupling parameters.

Spin excitations in 3D molecular magnets probed by neutron scattering

CERN Document Server

Bordallo, H N; Chapon, L C; Manson, J L; Cook, J C; Lee, S H; Copley, J R D; Yildirim, T; Kern, S

2002-01-01

The emerging field of molecular magnetism constitutes a new branch of materials science that deals with the magnetic properties of molecules, or assemblies of molecules, that contain magnetic centers. The growing interest in understanding the origin of the magnetic ordering in these materials is to obtain novel multiproperty molecular magnetic materials with high transition temperatures. Molecules based on the dicyanamide ion [N ident to C-N-C ident to N], abbreviated (dca), such as M(dca) sub 2 [M=Mn, Ni], have shown interesting bulk properties that prompted our inelastic neutron scattering (INS) studies. While the Mn sup 2 sup + ion is isotropic because of its L=0 configuration, the isostructural Ni analog has S=1 and demonstrates marked single-ion anisotropy. Mn(dca) sub 2 is a canted antiferromagnet below 16 K, while Ni(dca) sub 2 is a ferromagnet below 21 K. INS has been used to investigate the magnetic excitations in Mn(dca) sub 2 and Ni(dca) sub 2. For Mn(dca) sub 2 , a Heisenberg model gives good corr...

Electron-impact excitation and recombination of molecular cations in edge fusion plasma: application to H2+and BeD+

Science.gov (United States)

Pop, Nicolina; Iacob, Felix; Mezei, Zsolt; Motapon, Ousmanou; Niyonzima, Sebastien; Schneider, Ioan

2017-10-01

Dissociative recombination, ro-vibrational excitation and dissociative excitation of molecular cations with electrons are major elementary process in the kinetics and in the energy balance of astrophysically-relevant ionized media (supernovae, interstellar molecular clouds, planetary ionospheres, early Universe), in edge fusion and in many other cold media of technological interest. For the fusion plasma edge, extensive cross sections and rate coefficients have been produced for reactions induced on HD+, H2+ and BeD+ using the Multichannel Quantum Defect Theory (MQDT). Our calculations resulted in good agreement with the CRYRING (Stockholm) and TSR (Heidelberg) magnetic storage ring results, and our approach is permanently improved in order to face the new generation of electrostatic storage rings, as CSR (Heidelberg) and DESIREE (Stockholm). Member of APS Reciprocal Society: European Physics Society.

Energy relaxation in IR laser excited Hg1-xCdxTe

International Nuclear Information System (INIS)

Storebo, A K; Brudevoll, T; Olsen, O; Norum, O C; Breivik, M

2009-01-01

IR laser excitation of Hg l-x Cd x Te by low-fluence femtosecond and high fluence microsecond pulses was explored for the technologically important alloy fractions x ∼ 0.2 and x ∼ 0.28. We have used first principles (LAPW) electronic structure calculations and finite element modelling, supported by Monte Carlo simulation for the description of femtosecond pulse carrier relaxation and the transport parameters. Laser wavelengths considered were 6.4 - 10.6 μm for x ∼ 0.2 and 3.8 - 4.8 μm for x ∼ 0.28, with an incident 1 microsecond pulse fluence of 2 J/cm 2 . Many energy transfer mechanisms are invoked due to the long timescales of the microsecond pulses, and a main challenge is therefore to elucidate how these interplay in situations away from thermal equilibrium. Mechanisms studied include one- and two-photon absorption (OPA and TPA) across the band gap, inter-valence band absorption (IVA) between light- and heavy hole bands, electron-hole recombination/impact ionization, band gap renormalisation, intra-band free carrier absorption (FCA), excess carrier temperatures, non-equilibrium phonon generation, and refractive index changes. In the high fluence case, lattice temperatures evolve considerably during the laser pulse in response to the heated carriers. The chosen photon energies lie just above the band gap at the starting lattice temperature of 77 K, and nonlinear effects therefore dominate as the material heats up and the band gap begins to exceed the photon energy. Because of the low photon energy we must rely on Auger recombination, inter-valence band absorption and free carrier absorption to heat the carrier plasma. Although some Hg l-x Cd x Te material parameters are now relatively well known, existing data for many of the processes are inadequate for cases far away from thermal equilibrium. Furthermore, the role of Auger recombination in relation to non-intrinsic recombination has been a matter of debate lately. In this respect, information from

IR and visible luminescence studies in the infrared multiphoton dissociation of 1,2-dibromo-1,1-difluoroethane

Science.gov (United States)

Pushpa, K. K.; Kumar, Awadhesh; Vatsa, R. K.; Naik, P. D.; Annaji Rao, K.; Mittal, J. P.; Parthasarathy, V.; Sarkar, S. K.

1995-07-01

The infrared multiphoton dissociation of 1,2-dibromo-1,1-difluoroethane gives rise to IR and visible luminescence. Vibrationally excited parent molecules dissociate via two primary channels yielding bromine and vibrationally excited HBr. The strong visible emission observed between 350 to 750 nm has been assigned to electronically excited carbene CF 2Br CH.

Strategies to enhance the excitation energy-transfer efficiency in a light-harvesting system using the intra-molecular charge transfer character of carotenoids

Energy Technology Data Exchange (ETDEWEB)

Yukihira, Nao [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Sugai, Yuko [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Fujiwara, Masazumi [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Kosumi, Daisuke [Institute of Pulsed Power Science; Kumamoto University; Kumamoto; Japan; Iha, Masahiko [South Product Co. Ltd.; Uruma-shi; Japan; Sakaguchi, Kazuhiko [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Katsumura, Shigeo [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Gardiner, Alastair T. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Cogdell, Richard J. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Hashimoto, Hideki [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan

2017-01-01

Fucoxanthin is a carotenoid that is mainly found in light-harvesting complexes from brown algae and diatoms. Due to the presence of a carbonyl group attached to polyene chains in polar environments, excitation produces an excited intra-molecular charge transfer. This intra-molecular charge transfer state plays a key role in the highly efficient (~95%) energy-transfer from fucoxanthin to chlorophyllain the light-harvesting complexes from brown algae. In purple bacterial light-harvesting systems the efficiency of excitation energy-transfer from carotenoids to bacteriochlorophylls depends on the extent of conjugation of the carotenoids. In this study we were successful, for the first time, in incorporating fucoxanthin into a light-harvesting complex 1 from the purple photosynthetic bacterium,Rhodospirillum rubrumG9+ (a carotenoidless strain). Femtosecond pump-probe spectroscopy was applied to this reconstituted light-harvesting complex in order to determine the efficiency of excitation energy-transfer from fucoxanthin to bacteriochlorophyllawhen they are bound to the light-harvesting 1 apo-proteins.

Excited Landau levels, orbital angular momentum and axial anomaly

International Nuclear Information System (INIS)

Teryaev, O.V.

1993-01-01

The IR cutoff via the exclusion of the high orbital momentum components for the excited Landau levels leads to the physical interpretation of the cancellation between the explicity and anomalous chiral symmetry breaking. 21 refs

Electronic-excitation energy transfer in heterogeneous dye solutions under laser excitation

International Nuclear Information System (INIS)

Levshin, L.V.; Mukushev, B.T.; Saletskii, A.M.

1995-01-01

An experimental study has been made of electronic-excitation energy transfer (EEET) among dye molecules of different types for different exciting-fight wavelengths and temperatures. Upon selective laser excitation of the donor, the inhomogeneous broadening of molecular levels increases the probability of EEET from the donor to acceptor molecules. The efficiency of this process is directly proportional to the acceptor molecule concentration and is temperature dependent. The EEET is accompanied by the spectral migration of energy among donor molecules, which reduces the fluorescence quantum efficiency of the donor. Increasing the frequency of the exciting light decreases in the donor fluorescence quantum efficiency. An increase in the acceptor molecule concentration results in a decrease of the spectral migration of excitation in the donor molecule system. 5 refs., 5 figs

How does the plasmonic enhancement of molecular absorption depend on the energy gap between molecular excitation and plasmon modes: a mixed TDDFT/FDTD investigation.

Science.gov (United States)

Sun, Jin; Li, Guang; Liang, WanZhen

2015-07-14

A real-time time-dependent density functional theory coupled with the classical electrodynamics finite difference time domain technique is employed to systematically investigate the optical properties of hybrid systems composed of silver nanoparticles (NPs) and organic adsorbates. The results demonstrate that the molecular absorption spectra throughout the whole energy range can be enhanced by the surface plasmon resonance of Ag NPs; however, the absorption enhancement ratio (AER) for each absorption band differs significantly from the others, leading to the quite different spectral profiles of the hybrid complexes in contrast to those of isolated molecules or sole NPs. Detailed investigations reveal that the AER is sensitive to the energy gap between the molecular excitation and plasmon modes. As anticipated, two separate absorption bands, corresponding to the isolated molecules and sole NPs, have been observed at a large energy gap. When the energy gap approaches zero, the molecular excitation strongly couples with the plasmon mode to form the hybrid exciton band, which possesses the significantly enhanced absorption intensity, a red-shifted peak position, a surprising strongly asymmetric shape of the absorption band, and the nonlinear Fano effect. Furthermore, the dependence of surface localized fields and the scattering response functions (SRFs) on the geometrical parameters of NPs, the NP-molecule separation distance, and the external-field polarizations has also been depicted.

Continuum emission of excited sodium dimer

International Nuclear Information System (INIS)

Pardo, A.; Poyato, J.M.L.; Alonso, J.I.; Rico, F.R.

1980-01-01

A study has been made of the behaviour of excited molecular sodium using high-power Ar + laser radiation. A continuum emission was observed in the red wavelength region. This emission was thought to be caused by the formation of excited triatomic molecules. Energy transfer was observed from excited molecules to atoms. (orig.)

Comparison of Cherenkov excited fluorescence and phosphorescence molecular sensing from tissue with external beam irradiation.

Science.gov (United States)

Lin, Huiyun; Zhang, Rongxiao; Gunn, Jason R; Esipova, Tatiana V; Vinogradov, Sergei; Gladstone, David J; Jarvis, Lesley A; Pogue, Brian W

2016-05-21

Ionizing radiation delivered by a medical linear accelerator (LINAC) generates Cherenkov emission within the treated tissue. A fraction of this light, in the 600-900 nm wavelength region, propagates through centimeters of tissue and can be used to excite optical probes in vivo, enabling molecular sensing of tissue analytes. The success of isolating the emission signal from this Cherenkov excitation background is dependent on key factors such as: (i) the Stokes shift of the probe spectra; (ii) the excited state lifetime; (iii) the probe concentration; (iv) the depth below the tissue surface; and (v) the radiation dose used. Previous studies have exclusively focused on imaging phosphorescent dyes, rather than fluorescent dyes. However there are only a few biologically important phosphorescent dyes and yet in comparison there are thousands of biologically relevant fluorescent dyes. So in this study the focus was a study of efficacy of Cherenkov-excited luminescence using fluorescent commercial near-infrared probes, IRDye 680RD, IRDye 700DX, and IRDye 800CW, and comparing them to the well characterized phosphorescent probe Oxyphor PtG4, an oxygen sensitive dye. Each probe was excited by Cherenkov light from a 6 MV external radiation beam, and measured in continuous wave or time-gated modes. The detection was performed by spectrally resolving the luminescence signals, and measuring them with spectrometer-based separation on an ICCD detector. The results demonstrate that IRDye 700DX and PtG4 allowed for the maximal signal to noise ratio. In the case of the phosphorescent probe, PtG4, with emission decays on the microsecond (μs) time scale, time-gated acquisition was possible, and it allowed for higher efficacy in terms of the probe concentration and detection depth. Phantoms containing the probe at 5 mm depth could be detected at concentrations down to the nanoMolar range, and at depths into the tissue simulating phantom near 3 cm. In vivo studies showed that 5

Measurement of IR optics with linear coupling’s action-angle parametrization

Directory of Open Access Journals (Sweden)

Y. Luo

2005-08-01

Full Text Available Linear coupling’s action-angle parametrization is convenient for interpretation of turn-by-turn beam position monitor (BPM data. We demonstrate how to apply this parametrization to extract Twiss and coupling parameters in interaction regions (IRs, using BPMs on each side of a long IR drift region. Example data were acquired at the Relativistic Heavy Ion Collider, using an ac dipole to excite a single transverse eigenmode. We have measured the waist of the β function and its Twiss and coupling parameters.

Dual fluorescence of excited state intra-molecular proton transfer of HBFO: mechanistic understanding, substituent and solvent effects.

Science.gov (United States)

Yang, Wenjing; Chen, Xuebo

2014-03-07

A combined approach of the multiconfigurational perturbation theory with the Rice-Ramsperger-Kassel-Marcus methodology has been employed to calculate the minimum potential energy profiles and the rates of excited state intra-molecular proton transfer (ESIPT) for the WOLED material molecule of HBFO and its four meta- or para-substituted compounds in gas phase, acetonitrile and cyclohexane solvents. The kinetic control for these reactions is quantitatively determined and extensively studied on the basis of the accurate potential energy surfaces when the thermodynamic factor associated with the free energy change becomes negligible in the case of the existence of a significant barrier in the ESIPT process. These computational efforts contribute to a deep understanding of the ESIPT mechanism, dual emission characteristics, kinetic controlling factor, substituent and solvent effects for these material molecules. The white light emission is generated by the establishment of dynamic equilibrium between enol and keto forms in the charge transfer excited SCT((1)ππ*) state. The performance of white light emission is quantitatively demonstrated to be mainly sensitive to the molecular tailoring approach of the electronic properties of meta- or para- substituents by the modulation of the forward/backward ESIPT rate ratio. The quality of white light emission is slightly tunable through its surrounding solvent environment. These computational results will provide a useful strategy for the molecular design of OLED and WOLED materials.

Two-Magnon Raman Scattering and Pseudospin-Lattice Interactions in Sr_{2}IrO_{4} and Sr_{3}Ir_{2}O_{7}.

Science.gov (United States)

Gretarsson, H; Sung, N H; Höppner, M; Kim, B J; Keimer, B; Le Tacon, M

2016-04-01

We have used Raman scattering to investigate the magnetic excitations and lattice dynamics in the prototypical spin-orbit Mott insulators Sr_{2}IrO_{4} and Sr_{3}Ir_{2}O_{7}. Both compounds exhibit pronounced two-magnon Raman scattering features with different energies, line shapes, and temperature dependencies, which in part reflect the different influence of long-range frustrating exchange interactions. Additionally, we find strong Fano asymmetries in the line shapes of low-energy phonon modes in both compounds, which disappear upon cooling below the antiferromagnetic ordering temperatures. These unusual phonon anomalies indicate that the spin-orbit coupling in Mott-insulating iridates is not sufficiently strong to quench the orbital dynamics in the paramagnetic state.

Preparation of actinide targets by molecular plating for Coulomb excitation studies at ATLAS

International Nuclear Information System (INIS)

Greene, J. P.

1998-01-01

Molecular plating is now routinely used to prepare sources and targets of actinide elements. Although the technique is simple and fairly reproducible, because of the radioactive nature of the target it is very useful to record various parameters in the preparation of such targets. At Argonne, ∼200 microg/cm 2 thick targets of Pu and Cm were required for Coulomb Excitation (COULEX) Studies with the Argonne-Notre Dame BGO gamma ray facility and later with the GAMMASPHERE. These targets were plated on 50 mg/cm 2 Au backing and were covered with 150 microg/cm 2 Au foil. Targets of 239 Pu, 240 Pu, 242 Pu, 244 Pu and 248 Cm were prepared by dissolving the material in isopropyl alcohol and electroplating the actinide ions by applying 600 volts. The amount of these materials on the target was determined by alpha particle counting and gamma ray counting. Details of the molecular plating and counting will be discussed

Dissociative Excitation of Acetylene Induced by Electron Impact: Excitation-emission Cross-sections

Energy Technology Data Exchange (ETDEWEB)

Országh, Juraj; Danko, Marián; Čechvala, Peter; Matejčík, Štefan, E-mail: matejcik@fmph.uniba.sk [Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University in Bratislava, Mlynská dolina F-2, 842 48 Bratislava (Slovakia)

2017-05-20

The optical emission spectrum of acetylene excited by monoenergetic electrons was studied in the range of 190–660 nm. The dissociative excitation and dissociative ionization associated with excitation of the ions initiated by electron impact were dominant processes contributing to the spectrum. The spectrum was dominated by the atomic lines (hydrogen Balmer series, carbon) and molecular bands (CH(A–X), CH(B–X), CH{sup +}(B–A), and C{sub 2}). Besides the discrete transitions, we have detected the continuum emission radiation of ethynyl radical C{sub 2}H(A–X). For most important lines and bands of the spectrum we have measured absolute excitation-emission cross sections and determined the energy thresholds of the particular dissociative channels.

Espectroscopía Espacial en el IR-Lejano

Science.gov (United States)

Goicoechea, Javier R.; Cernicharo, J.

Debido a la opacidad atmosférica, el dominio IR--lejano del espectro electromagnético ha sido la última ventana en ser utilizada por la Astrofísica Molecular. El potencial que supone abrir este nuevo rango de frecuencias a través de la espectroscopía molecular ha comenzado a ser explotado con el Infrared Space Observatory (ISO). La sensibilidad de la instrumentación embarcada en dicho satélite no tiene comparación alguna con las escasas misiones espaciales, o a bordo de aviones, realizadas con anterioridad a su lanzamiento. En particular, casi todo el rango operativo de ISO en el IR--lejano no había sido explorado. El espectro IR--lejano de las fuentes más representativas de la galaxia era desconocido y los principales emisores de radiación, las moléculas, estaban por identificar. Las observaciones en el IR--lejano están especialmente indicadas para el estudio del gas caliente en las nubes moleculares del medio interestelar y en el interior de las envolturas circunestelares alrededor de estrellas evolucionadas. Algunas de estas fuentes; Sgr B2 en el Centro Galáctico y las Proto--Nebulosas Planetarias, constituyen uno de los objetos más paradigmáticos en nuestra comprensión de la complejidad química de La Galaxia. En esta contribución se presentan los resultados espectroscópicos más importantes de algunas de estas fuentes astronómicas.

Superluminal travel, UV/IR mixing, and turbulence in a (1+1)-dimensional world

International Nuclear Information System (INIS)

Dubovsky, Sergei; Gorbenko, Victor

2011-01-01

We study renormalizable Lorentz invariant stable quantum field theories in two space-time dimensions with instantaneous causal structure (causal ordering induced by the light 'cone' time ordering). These models provide a candidate UV completion of the two-dimensional ghost condensate. They exhibit a peculiar UV/IR mixing - energies of all excitations become arbitrarily small at high spatial momenta. We discuss several phenomena associated with this mixing. These include the impossibility to reach a thermal equilibrium and metastability of all excitations towards decay into short-wavelength modes resulting in an indefinite turbulent cascade. In spite of the UV/IR mixing in many cases the UV physics can still be decoupled from low-energy phenomena. However, a patient observer in the Lineland is able to produce arbitrarily heavy particles simply by waiting for a long enough time.

First-principles study of molecular NO dissociation on Ir(100) surface

Science.gov (United States)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2014-02-01

The dissociation of NO on Ir(100) surface is investigated using density functional theory (DFT). The pathway and transition state (TS) of the dissociation of NO molecule are determined using climbing image nudge elastic band (CI-NEB). The prerequisite state of NO dissociation is determining the most stable sites of the reactant and products. We found that the most energetically stable sites are the hollow for N atom and the bridge for NO molecule as well as O atom. We found that the bending of NO is the first step of the dissociation reaction due to the increase of the back-donation from the d-band of Ir to 2 π ∗ orbital of NO, which causes the weakening of NO bond. The dissociation energy barrier of NO molecule on Ir(100) surface is 0.49 eV.

Capturing molecular multimode relaxation processes in excitable gases based on decomposition of acoustic relaxation spectra

Science.gov (United States)

Zhu, Ming; Liu, Tingting; Wang, Shu; Zhang, Kesheng

2017-08-01

Existing two-frequency reconstructive methods can only capture primary (single) molecular relaxation processes in excitable gases. In this paper, we present a reconstructive method based on the novel decomposition of frequency-dependent acoustic relaxation spectra to capture the entire molecular multimode relaxation process. This decomposition of acoustic relaxation spectra is developed from the frequency-dependent effective specific heat, indicating that a multi-relaxation process is the sum of the interior single-relaxation processes. Based on this decomposition, we can reconstruct the entire multi-relaxation process by capturing the relaxation times and relaxation strengths of N interior single-relaxation processes, using the measurements of acoustic absorption and sound speed at 2N frequencies. Experimental data for the gas mixtures CO2-N2 and CO2-O2 validate our decomposition and reconstruction approach.

Benchmarking the stochastic time-dependent variational approach for excitation dynamics in molecular aggregates

Energy Technology Data Exchange (ETDEWEB)

Chorošajev, Vladimir [Department of Theoretical Physics, Faculty of Physics, Vilnius University, Sauletekio 9-III, 10222 Vilnius (Lithuania); Gelzinis, Andrius; Valkunas, Leonas [Department of Theoretical Physics, Faculty of Physics, Vilnius University, Sauletekio 9-III, 10222 Vilnius (Lithuania); Department of Molecular Compound Physics, Center for Physical Sciences and Technology, Sauletekio 3, 10222 Vilnius (Lithuania); Abramavicius, Darius, E-mail: darius.abramavicius@ff.vu.lt [Department of Theoretical Physics, Faculty of Physics, Vilnius University, Sauletekio 9-III, 10222 Vilnius (Lithuania)

2016-12-20

Highlights: • The Davydov ansatze can be used for finite temperature simulations with an extension. • The accuracy is high if the system is strongly coupled to the environmental phonons. • The approach can simulate time-resolved fluorescence spectra. - Abstract: Time dependent variational approach is a convenient method to characterize the excitation dynamics in molecular aggregates for different strengths of system-bath interaction a, which does not require any additional perturbative schemes. Until recently, however, this method was only applicable in zero temperature case. It has become possible to extend this method for finite temperatures with the introduction of stochastic time dependent variational approach. Here we present a comparison between this approach and the exact hierarchical equations of motion approach for describing excitation dynamics in a broad range of temperatures. We calculate electronic population evolution, absorption and auxiliary time resolved fluorescence spectra in different regimes and find that the stochastic approach shows excellent agreement with the exact approach when the system-bath coupling is sufficiently large and temperatures are high. The differences between the two methods are larger, when temperatures are lower or the system-bath coupling is small.

Symmetry characterization of electrons and lattice excitations

Directory of Open Access Journals (Sweden)

Schober H.

2012-03-01

Full Text Available Symmetry concerns all aspects of a physical system from the electronic orbitals to structural and magnetic excitations. In this article we will try to elaborate the fundamental connection between symmetry and excitations. As excitations are manyfold in physical systems it is impossible to treat them exhaustively. We thus concentrate on the two topics of Bloch electrons and phonons. These two examples are complementary in the sense that Bloch electrons describe single particles in an external periodic potential while phonons exemplify a decoupled system of interacting particles. The way we develop the argument gives as by-product a short account of molecular orbitals and molecular vibrations.

Cavitation and shock waves emission on the rigid boundary of water under mid-IR nanosecond laser pulse excitation

Science.gov (United States)

Pushkin, A. V.; Bychkov, A. S.; Karabutov, A. A.; Potemkin, F. V.

2018-06-01

The processes of conversion of light energy into mechanical energy under mid-IR nanosecond laser excitation on a rigid boundary of water are investigated. Strong water absorption of Q-switched Cr:Yb:Ho:YSGG (2.85 µm, 6 mJ, 45 ns) laser radiation provides rapid energy deposition of ~8 kJ cm‑3 accompanied with strong mechanical transients. The evolution of shock waves and cavitation bubbles is studied using the technique of shadowgraphy and acoustic measurements, and the conversion efficiency into these energy channels for various laser fluence (0.75–2.0 J cm‑2) is calculated. For 6 mJ laser pulse with fluence of 2.0 J cm‑2, the conversion into shock wave energy reaches 67%. The major part of the shock wave energy (92%) is dissipated when the shock front travels the first 250 µm, and the remaining 8% is transferred to the acoustic far field. The calculated pressure in the vicinity of water-silicon interface is 0.9 GPa. Cavitation efficiency is significantly less and reaches up to 5% of the light energy. The results of the current study could be used in laser parameters optimization for micromachining and biological tissue ablation.

Physical Meaning of Virtual Kohn-Sham Orbitals and Orbital Energies: An Ideal Basis for the Description of Molecular Excitations.

Science.gov (United States)

van Meer, R; Gritsenko, O V; Baerends, E J

2014-10-14

In recent years, several benchmark studies on the performance of large sets of functionals in time-dependent density functional theory (TDDFT) calculations of excitation energies have been performed. The tested functionals do not approximate exact Kohn-Sham orbitals and orbital energies closely. We highlight the advantages of (close to) exact Kohn-Sham orbitals and orbital energies for a simple description, very often as just a single orbital-to-orbital transition, of molecular excitations. Benchmark calculations are performed for the statistical average of orbital potentials (SAOP) functional for the potential [J. Chem. Phys. 2000, 112, 1344; 2001, 114, 652], which approximates the true Kohn-Sham potential much better than LDA, GGA, mGGA, and hybrid potentials do. An accurate Kohn-Sham potential does not only perform satisfactorily for calculated vertical excitation energies of both valence and Rydberg transitions but also exhibits appealing properties of the KS orbitals including occupied orbital energies close to ionization energies, virtual-occupied orbital energy gaps very close to excitation energies, realistic shapes of virtual orbitals, leading to straightforward interpretation of most excitations as single orbital transitions. We stress that such advantages are completely lost in time-dependent Hartree-Fock and partly in hybrid approaches. Many excitations and excitation energies calculated with local density, generalized gradient, and hybrid functionals are spurious. There is, with an accurate KS, or even the LDA or GGA potentials, nothing problematic about the "band gap" in molecules: the HOMO-LUMO gap is close to the first excitation energy (the optical gap).

Electronic [UV-Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR-mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations

Science.gov (United States)

Karthikeyan, N.; Joseph Prince, J.; Ramalingam, S.; Periandy, S.

2015-03-01

In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid (TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data related to base molecule and substitutional group of the compound was analyzed. The modification of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The 13C and 1H NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with experimental spectra. The study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to atomic mass and the mass variation depends on the substitutions have also been studied.

Luminescence of Er3+ doped double lead halide crystals under X-ray, UV, VIS and IR excitation

Science.gov (United States)

Serazetdinov, A. R.; Smirnov, A. A.; Pustovarov, V. A.; Isaenko, L. I.

2017-09-01

Er3+ doped double lead halide crystals incorporate a number of properties making them interesting for practical use in light conducting materials. X-ray excited luminescence (XRL) spectra, photoluminescence (PL) spectra in region of 1.5-3.5 eV, photoluminescence excitation (PLE) spectra (2.75-5 eV) and anti-stokes luminescence (ASL) spectra were measured at room temperature in KPb2Cl5 (KPC) and RbPb2Br5 (RPB) matrices doped with Er3+ (1%) ions and in KPC doped with Er3++ Yb3+ ions(1:3 ratio concentration). Intraconfigurational f→f transitions are observed in Er3+ ions in most of the cases. The concrete spectrum form is strongly dependent on the excitation energy. Under 980 nm excitation upper Er3+ levels are excited, showing upconversional processes. In case of 313 nm (UV) and 365 nm (VIS) excitation self trapped exciton luminescence was detected in RPB crystal. Additional Yb3+ doping ions strongly increase quantum yield under 980 nm excitation and this doping cause insignificant influence on quantum yield under VIS or UV excitation.

Low-energy levels calculation for 193Ir

International Nuclear Information System (INIS)

Zahn, Guilherme Soares; Zamboni, Cibele Bugno; Genezini, Frederico Antonio; Mesa-Hormaza, Joel; Cruz, Manoel Tiago Freitas da

2006-01-01

In this work, a model based on single particle plus pairing residual interaction was used to study the low-lying excited states of the 193 Ir nucleus. In this model, the deformation parameters in equilibrium were obtained by minimizing the total energy calculated by the Strutinsky prescription; the macroscopic contribution to the potential was taken from the Liquid Droplet Model, with the shell and paring corrections used as as microscopic contributions. The nuclear shape was described using the Cassinian ovoids as base figures; the single particle energy spectra and wave functions for protons and neutrons were calculated in a deformed Woods-Saxon potential, where the parameters for neutrons were obtained from the literature and the parameters for protons were adjusted in order to describe the main sequence of angular momentum and parity of the band heads, as well as the proton binding energy of 193 Ir. The residual pairing interaction was calculated using the BCS prescription with Lipkin-Nogami approximation. The results obtained for the first three band heads (the 3/2 + ground state, the 1/2 + excited state at E ∼ 73 keV and the the 11/2 - isomeric state at E ∼ 80 keV) showed a very good agreement, but the model so far greatly overestimated the energy of the next band head, a 7/2 - at E ∼ 299 keV. (author)

What Lurks in ULIRGs?—Probing the Chemistry and Excitation of Molecular Gas in the Nuclei of Arp 220 and NGC 6240

Energy Technology Data Exchange (ETDEWEB)

Manohar, Swarnima; Scoville, Nick [California Institute of Technology, MC 249-17, 1200 East California Boulevard, Pasadena, CA 91125 (United States)

2017-02-01

We have imaged the dense star-forming regions of Arp 220 and NGC 6240 in the 3 mm band transitions of CO, HCN, HCO{sup +}, HNC, and CS at 0.″5–0.″8 resolution using CARMA. Our data set images all these lines at similar resolutions and high sensitivity, and can be used to derive line ratios of faint high excitation lines. In both the nuclei of Arp 220, the HCN/HNC ratios suggest chemistry of X-ray Dominated Regions (XDRs)—a likely signature of an active galactic nucleus. In NGC 6240, there is no evidence of XDR type chemistry, but there the bulk of the molecular gas is concentrated between the nuclei rather than on them. We calculated molecular H{sub 2} densities from excitation analysis of each of the molecular species. It appears that the abundances of HNC and HCO{sup +} in Ultra Luminous Infrared Galaxies may be significantly different from those in galactic molecular clouds. The derived H{sub 2} volume densities are ∼5 × 10{sup 4} cm{sup −3} in the Arp 220 nuclei and ∼10{sup 4} cm{sup −3} in NGC 6240.

Excited State Spectra and Dynamics of Phenyl-Substituted Butadienes

DEFF Research Database (Denmark)

Wallace-Williams, Stacie E.; Schwartz, Benjamin J.; Møller, Søren

1994-01-01

indicate that phenyl torsional motion is not important to the excited-state dynamics and reveal alternative excited-state reaction pathways. The results demonstrate how molecular systems that are structually similar can exhibit different electronic properties and excited-state dynamics....

PERIODIC ACCRETION INSTABILITIES IN THE PROTOSTAR L1634 IRS 7

Energy Technology Data Exchange (ETDEWEB)

Hodapp, Klaus W. [Institute for Astronomy, University of Hawaii, 640 N. Aohoku Place, Hilo, HI 96720 (United States); Chini, Rolf, E-mail: hodapp@ifa.hawaii.edu, E-mail: rolf.chini@astro.ruhr-uni-bochum.de [Astronomisches Institut, Ruhr-Universität Bochum, Universitätsstraße 150, D-44801 Bochum (Germany)

2015-11-10

The small molecular cloud Lynds 1634 contains at least three outflow sources. We found one of these, IRS 7, to be variable with a period of 37.14 ± 0.04 days and an amplitude of approximately 2 mag in the K{sub s} band. The light curve consists of a quiescent phase with little or no variation, and a rapid outburst phase. During the outburst phase, the rapid variation in brightness generates light echoes that propagate into the surrounding molecular cloud, allowing a measurement of the distance to IRS 7 of 404 pc ± 35 pc. We observed only a marginally significant change in the H − K color during the outburst phase. The K-band spectrum of IRS 7 shows CO bandhead emission but its equivalent width does not change significantly with the phase of the light curve. The H{sub 2} 1–0 S(1) line emission does not follow the variability of the continuum flux. We also used the imaging data for a proper motion study of the outflows originating from the IRS 7 and the far-infrared source IRAS 05173-0555, and confirm that these are indeed distinct outflows.

DIRECT IMAGING OF A COMPACT MOLECULAR OUTFLOW FROM A VERY LOW LUMINOSITY OBJECT: L1521F-IRS

Energy Technology Data Exchange (ETDEWEB)

Takahashi, Satoko [Joint ALMA Observatory, Alonso de Cordova 3107, Vitacura, Santiago (Chile); Ohashi, Nagayoshi [Academia Sinica Institute of Astronomy and Astrophysics, P.O. Box 23-141, Taipei 10617, Taiwan (China); Bourke, Tyler L., E-mail: satoko.takahashi@nao.ac.jp [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

2013-09-01

Studying the physical conditions of very low luminosity objects (VeLLOs; L{sub bol} < 0.1 L{sub Sun }) is important for understanding the earliest evolutionary stage of protostars and brown dwarfs. We report interferometric observations of the VeLLO L1521F-IRS, in {sup 12}CO (2-1) line emission and the 1.3 mm continuum emission, using the Submillimeter Array. With the {sup 12}CO (2-1) high-resolution observations, we have spatially resolved a compact but poorly collimated molecular outflow associated with L1521F-IRS for the first time. The blueshifted and redshifted lobes are aligned along the east and west side of L1521F-IRS with a lobe size of Almost-Equal-To 1000 AU. The estimated outflow mass, maximum outflow velocity, and outflow force are (9.0-80) Multiplication-Sign 10{sup -4} M{sub Sun }, 7.2 km s{sup -1}, and (7.4-66) Multiplication-Sign 10{sup -7} M{sub Sun} km s{sup -1} yr{sup -1}, respectively. The estimated outflow parameters such as size, mass, and momentum rate are similar to values derived for other VeLLOs, and are located at the lower end of values compared to previously studied outflows associated with low- to high-mass star-forming regions. Low-velocity less collimated (1.5 km s{sup -1}/1200 AU) and higher-velocity compact (4.0 km s{sup -1}/920 AU) outflow components are suggested by the data. These velocity structures are not consistent with those expected in the jet-driven or wind-driven outflow models, perhaps suggesting a remnant outflow from the first hydrostatic core as well as an undeveloped outflow from the protostar. Detection of an infrared source and compact millimeter continuum emission suggests the presence of the protostar, while its low bolometric luminosity (0.034-0.07 L{sub Sun }) and small outflow suggests that L1521F is in the earliest protostellar stage (<10{sup 4} yr) and contains a substellar mass object. The bolometric (or internal) luminosity of L1521F-IRS suggests that the current mass accretion rate is an order of

IR OPTICS MEASUREMENT WITH LINEAR COUPLING'S ACTION-ANGLE PARAMETERIZATION

International Nuclear Information System (INIS)

LUO, Y.; BAI, M.; PILAT, R.; SATOGATA, T.; TRBOJEVIC, D.

2005-01-01

A parameterization of linear coupling in action-angle coordinates is convenient for analytical calculations and interpretation of turn-by-turn (TBT) beam position monitor (BPM) data. We demonstrate how to use this parameterization to extract the twiss and coupling parameters in interaction regions (IRs), using BPMs on each side of the long IR drift region. The example of TBT BPM analysis was acquired at the Relativistic Heavy Ion Collider (RHIC), using an AC dipole to excite a single eigenmode. Besides the full treatment, a fast estimate of beta*, the beta function at the interaction point (IP), is provided, along with the phase advance between these BPMs. We also calculate and measure the waist of the beta function and the local optics

Impaired Insulin Signaling is Associated with Hepatic Mitochondrial Dysfunction in IR+/−-IRS-1+/− Double Heterozygous (IR-IRS1dh Mice

Directory of Open Access Journals (Sweden)

Andras Franko

2017-05-01

Full Text Available Mitochondria play a pivotal role in energy metabolism, but whether insulin signaling per se could regulate mitochondrial function has not been identified yet. To investigate whether mitochondrial function is regulated by insulin signaling, we analyzed muscle and liver of insulin receptor (IR+/−-insulin receptor substrate-1 (IRS-1+/− double heterozygous (IR-IRS1dh mice, a well described model for insulin resistance. IR-IRS1dh mice were studied at the age of 6 and 12 months and glucose metabolism was determined by glucose and insulin tolerance tests. Mitochondrial enzyme activities, oxygen consumption, and membrane potential were assessed using spectrophotometric, respirometric, and proton motive force analysis, respectively. IR-IRS1dh mice showed elevated serum insulin levels. Hepatic mitochondrial oxygen consumption was reduced in IR-IRS1dh animals at 12 months of age. Furthermore, 6-month-old IR-IRS1dh mice demonstrated enhanced mitochondrial respiration in skeletal muscle, but a tendency of impaired glucose tolerance. On the other hand, 12-month-old IR-IRS1dh mice showed improved glucose tolerance, but normal muscle mitochondrial function. Our data revealed that deficiency in IR/IRS-1 resulted in normal or even elevated skeletal muscle, but impaired hepatic mitochondrial function, suggesting a direct cross-talk between insulin signaling and mitochondria in the liver.

Cold excitation and determination of hydrogen sulfide by dielectric barrier discharge molecular emission spectrometry.

Science.gov (United States)

Wu, Zhongchen; Jiang, Jie; Li, Na

2015-11-01

A low-temperature microplasma generated in a dielectric barrier discharge (DBD) was used as a radiation source for the excitation of hydrogen sulfide and its determination by molecular emission spectrometry (MES). The excitation/emission chamber was enclosed to eliminate spectral interference from ambient air. The spectral emission lines of hydrogen sulfide were clearly discriminated from the background spectrum, and the emission line at 365.06 nm was selected for parameter optimization and quantitative analysis. The S(2-) ions in aqueous samples were reacted with acid to generate hydrogen sulfide and then determined. The experimental parameters affecting the determination of hydrogen sulfide and S(2-) were optimized. The limits of detection were 1.4 mg m(-3) for H2S and 11.2 mg L(-1) for S(2-). The repeatability of the method was satisfactory, as the RSD values were 2.3% for H2S and 1.8% for S(2-). The enclosed DBD-MES system was demonstrated to be a useful tool for the determination of hydrogen sulfide in gas samples and S(2-) in aqueous samples. Copyright © 2015 Elsevier B.V. All rights reserved.

ESR studies of electron irradiated K3Ir(CN)6 in KCl single crystals

International Nuclear Information System (INIS)

Vugman, N.V.; Pinhal, N.M.

1983-01-01

ESR studies of KCl single crystals doped with small amounts of K 3 Ir(CN) 6 and submitted to a prolongued 2 MeV electron irradiation at room temperature reveal the presence of the [IR(CN) 5 Cl] 4- and [Ir(CN) 4 Cl 2 ] 4- new molecular species. Ligand spin densities and ligand field parameters are calculated from the experimental hyperfine and superhyperfine interactions and compared to previous data on the [Ir(CN) 5 ] 4- species. (Author) [pt

A study of the region of massive star formation L379IRS1 in radio lines of methanol and other molecules

Science.gov (United States)

Kalenskii, S. V.; Shchurov, M. A.

2016-04-01

The results of spectral observations of the region of massive star formation L379IRS1 (IRAS18265-1517) are presented. The observations were carried out with the 30-m Pico Veleta radio telescope (Spain) at seven frequencies in the 1-mm, 2-mm, and 3-mm wavelength bands. Lines of 24 molecules were detected, from simple diatomic or triatomic species to complex eight- or nine-atom compounds such as CH3OCHO or CH3OCH3. Rotation diagrams constructed from methanol andmethyl cyanide lines were used to determine the temperature of the quiescent gas in this region, which is about 40-50 K. In addition to this warm gas, there is a hot component that is revealed through high-energy lines of methanol and methyl cyanide, molecular lines arising in hot regions, and the presence of H2O masers and Class II methanol masers at 6.7 GHz, which are also related to hot gas. One of the hot regions is probably a compact hot core, which is located near the southern submillimeter peak and is related to a group of methanol masers at 6.7 GHz. High-excitation lines at other positions may be associated with other hot cores or hot post-shock gas in the lobes of bipolar outflows. The rotation diagrams can be use to determine the column densities and abundances of methanol (10-9) and methyl cyanide (about 10-11) in the quiescent gas. The column densities of A- and E-methanol in L379IRS1 are essentually the same. The column densities of other observedmolecules were calculated assuming that the ratios of the molecular level abundances correspond to a temperature of 40 K. The molecular composition of the quiescent gas is close to that in another region of massive star formation, DR21(OH). The only appreciable difference is that the column density of SO2 in L379IRS1 is at least a factor of 20 lower than the value in DR21(OH). The SO2/CS and SO2/OCS abundance ratios, which can be used as chemical clocks, are lower in L379IRS1 than in DR21(OH), suggesting that L379IRS1 is probably younger than DR21(OH).

FT-IR microscopical analysis with synchrotron radiation: The microscope optics and system performance

International Nuclear Information System (INIS)

Reffner, J.A.; Martoglio, P.A.; Williams, G.P.

1995-01-01

When a Fourier transform infrared (FT-IR) microspectrometer was first interfaced with the National Synchrotron Light Source (NSLS) in September 1993, there was an instant realization that the performance at the diffraction limit had increased 40-100 times. The synchrotron source transformed the IR microspectrometer into a true IR microprobe, providing high-quality IR spectra for probe diameters at the diffraction limit. The combination of IR microspectroscopy and synchrotron radiation provides a powerful new tool for molecular spectroscopy. The ability to perform IR microspectroscopy with synchrotron radiation is still under development at Brookhaven National Laboratory, but several initial studies have been completed that demonstrate the broad-ranging applications of this technology and its potential for materials characterization

FT-IR microscopical analysis with synchrotron radiation: The microscope optics and system performance

Energy Technology Data Exchange (ETDEWEB)

Reffner, J.A.; Martoglio, P.A. [Spectra-Tech, Inc., Shelton, CT (United States); Williams, G.P. [Brookhaven National Lab., Upton, NY (United States)

1995-01-01

When a Fourier transform infrared (FT-IR) microspectrometer was first interfaced with the National Synchrotron Light Source (NSLS) in September 1993, there was an instant realization that the performance at the diffraction limit had increased 40-100 times. The synchrotron source transformed the IR microspectrometer into a true IR microprobe, providing high-quality IR spectra for probe diameters at the diffraction limit. The combination of IR microspectroscopy and synchrotron radiation provides a powerful new tool for molecular spectroscopy. The ability to perform IR microspectroscopy with synchrotron radiation is still under development at Brookhaven National Laboratory, but several initial studies have been completed that demonstrate the broad-ranging applications of this technology and its potential for materials characterization.

A Molecular and Cellular Context-Dependent Role for Ir76b in Detection of Amino Acid Taste

Directory of Open Access Journals (Sweden)

Anindya Ganguly

2017-01-01

Full Text Available Amino acid taste is expected to be a universal property among animals. Although sweet, bitter, salt, and water tastes have been well characterized in insects, the mechanisms underlying amino acid taste remain elusive. From a Drosophila RNAi screen, we identify an ionotropic receptor, Ir76b, as necessary for yeast preference. Using calcium imaging, we identify Ir76b+ amino acid taste neurons in legs, overlapping partially with sweet neurons but not those that sense other tastants. Ir76b mutants have reduced responses to amino acids, which are rescued by transgenic expression of Ir76b and a mosquito ortholog AgIr76b. Co-expression of Ir20a with Ir76b is sufficient for conferring amino acid responses in sweet-taste neurons. Notably, Ir20a also serves to block salt response of Ir76b. Our study establishes the role of a highly conserved receptor in amino acid taste and suggests a mechanism for mutually exclusive roles of Ir76b in salt- and amino-acid-sensing neurons.

Wall effect in deactivation of excited molecular oxygen {sup 1}{delta}g; Reiki sanso bunshi {sup 1}{delta}g no shikkatsu ni oyobosu hyomen hanno no eikyo

Energy Technology Data Exchange (ETDEWEB)

Takahashi, S.; Hasegawa, Y.; Yamashita, I. [Mechanical Engineering Laboratory, Tsukuba (Japan)

1993-10-25

This paper discusses effects of surface reaction on deactivation of excited molecular oxygen in {sup 1}{Delta}g condition. Gaseous oxygen containing excited oxygen generated by microwave discharge at a concentration of less than 1% is flown into several kinds of tubes to be measured such as quartz tubes (with an inner diameter of about 10 mm), and the light emitting intensity of the excited oxygen was measured upstream and downstream of the tubes to be measured (with in-tube pressure of 1 Torr or 2 Torr) to derive its concentration change. The surface reaction on the tube wall was regarded as a primary reaction, and the concentration change of the excited oxygen in flows in the round tube (attributable to the surface reaction) was analyzed. With respect to effects of tube wall materials on deactivation of the excited molecular oxygen, the surface deactivation probability in the case of using low-activity materials has decreased in the order of Pyrex, PVC, quartz, PFA and PTFE. The surface deactivation probability in the case of using a metallic material, SUS316L, was about 1000 times larger than that in the quartz. 14 refs., 7 figs., 1 tab.

Dust Processing in Supernova Remnants: Spitzer MIPS SED and IRS Observations

Science.gov (United States)

Hewitt, John W.; Petre, Robert; Katsuda Satoru; Andersen, M.; Rho, J.; Reach, W. T.; Bernard, J. P.

2011-01-01

We present Spitzer MIPS SED and IRS observations of 14 Galactic Supernova Remnants previously identified in the GLIMPSE survey. We find evidence for SNR/molecular cloud interaction through detection of [OI] emission, ionic lines, and emission from molecular hydrogen. Through black-body fitting of the MIPS SEDs we find the large grains to be warm, 29-66 K. The dust emission is modeled using the DUSTEM code and a three component dust model composed of populations of big grains, very small grains, and polycyclic aromatic hydrocarbons. We find the dust to be moderately heated, typically by 30-100 times the interstellar radiation field. The source of the radiation is likely hydrogen recombination, where the excitation of hydrogen occurred in the shock front. The ratio of very small grains to big grains is found for most of the molecular interacting SNRs to be higher than that found in the plane of the Milky Way, typically by a factor of 2--3. We suggest that dust shattering is responsible for the relative over-abundance of small grains, in agreement with prediction from dust destruction models. However, two of the SNRs are best fit with a very low abundance of carbon grains to silicate grains and with a very high radiation field. A likely reason for the low abundance of small carbon grains is sputtering. We find evidence for silicate emission at 20 $\\mu$m in their SEDs, indicating that they are young SNRs based on the strong radiation field necessary to reproduce the observed SEDs.

Laser separation of nitrogen isotopes by the IR+UV dissociation of ammonia molecules

International Nuclear Information System (INIS)

Apatin, V M; Klimin, S A; Laptev, V B; Lokhman, V N; Ogurok, D D; Pigul'skii, S V; Ryabov, E A

2008-01-01

The separation of nitrogen isotopes is studied upon successive single-photon IR excitation and UV dissociation of ammonia molecules. The excitation selectivity was provided by tuning a CO 2 laser to resonance with 14 NH 3 molecules [the 9R(30) laser line] or with 15 NH 3 molecules [the 9R(10) laser line]. Isotopic mixtures containing 4.8% and 0.37% (natural content) of the 15 NH isotope were investigated. The dependences of the selectivity and the dissociation yield for each isotopic component on the buffer gas pressure (N 2 , O 2 , Ar) and the ammonia pressure were obtained. In the limit of low NH 3 pressures (0.5-2 Torr), the dissociation selectivity α(15/14) for 15 N was 17. The selectivity mechanism of the IR+UV dissociation is discussed and the outlook is considered for the development of the nitrogen isotope separation process based on this approach. (laser isotope separation)

Preparation of actinide targets by molecular plating for coulomb excitation studies at ATLAS

CERN Document Server

Greene, J P; Ahmad, I

1999-01-01

Molecular plating is now routinely used to prepare sources and targets of actinide elements. Although the technique is simple and fairly reproducible, because of the radioactive nature of the targets, it is very useful to record various parameters in the preparation process. At Argonne, approx 200 mu g/cm sup 2 thick targets of Pu and Cm were required for Coulomb Excitation (COULEX) studies with the Argonne-Notre Dame boron germanate (BGO) gamma-ray facility and later with the GAMMASPHERE. These targets were plated on 50 mg/cm sup 2 Au backings and were covered with 150 mu g/cm sup 2 Au foil. Targets of sup 2 sup 3 sup 9 Pu, sup 2 sup 4 sup 0 Pu, sup 2 sup 4 sup 2 Pu, sup 2 sup 4 sup 4 Pu and sup 2 sup 4 sup 8 Cm were prepared by dissolving the material in isopropyl alcohol and electroplating the actinide ions by applying 600 V. The amount of these materials on the target was determined by alpha particle counting and gamma-ray counting. Details of the molecular plating and counting will be discussed.

Realisation and crossed molecular beams study of H2/O chemical reactions at several excited states

International Nuclear Information System (INIS)

Marx, Jacqueline

1986-01-01

This work is devoted to the study of the reactive collision O + H 2 OH + H in a crossed beam experiment. This process including several channels taken a part in the chemistry of the upper atmosphere as well as in the combustion of hydrogen. According to the electronic or vibrational state of the reactants, the OH radical is produced in its ground electronic state OH (X 2 π) or in its first excited state OH (A 2 Σ + ). When the reactants are in their ground state, the reaction is endothermic in the conditions of the experiment (center of mass kinetic energy ≅ 0.12 eV). The following reactions have been obtained: O( 1 D) +H 2 (v=O) → OH (X 2 π) +H( 2 S) and O( 1 D) +H 2 (v≥5) → OH (A 2 Σ + ) +H( 2 S). The atomic oxygen is produced in its excited state O( 1 D) in a radio-frequency discharge which dissociates the molecular oxygen seeded in a carrier gas (He or Ar) and the hydrogen molecules are excited vibrationally by electron bombardment. The first reaction is studied by time-of-flight measurements. In this way, it has been possible to observe the different vibrational levels on which the OH radical is produced. The analysis of this vibrational distribution shows the competition between the abstraction and insertion-dissociation mechanisms. In the second reaction, the analysis of the spontaneous fluorescence of OH (A 2 Σ + ) reveals a very hot and non-Boltzmann rotational excitation. (author) [fr

Stimulated emission depletion following two photon excitation

OpenAIRE

Marsh, R. J.; Armoogum, D. A.; Bain, A. J.

2002-01-01

The technique of stimulated emission depletion of fluorescence (STED) from a two photon excited molecular population is demonstrated in the S, excited state of fluorescein in ethylene glycol and methanol. Two photon excitation (pump) is achieved using the partial output of a regeneratively amplified Ti:Sapphire laser in conjunction with an optical parametric amplifier whose tuneable output provides a synchronous depletion (dump) pulse. Time resolved fluorescence intensity and anisotropy measu...

Electronic [UV-Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR-mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations.

Science.gov (United States)

Karthikeyan, N; Prince, J Joseph; Ramalingam, S; Periandy, S

2015-03-15

In this research work, the vibrational IR, polarization Raman, NMR and mass spectra of terephthalic acid (TA) were recorded. The observed fundamental peaks (IR, Raman) were assigned according to their distinctiveness region. The hybrid computational calculations were carried out for calculating geometrical and vibrational parameters by DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The molecular mass spectral data related to base molecule and substitutional group of the compound was analyzed. The modification of the chemical property by the reaction mechanism of the injection of dicarboxylic group in the base molecule was investigated. The (13)C and (1)H NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method and the absolute chemical shifts related to TMS were compared with experimental spectra. The study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by hybrid Gaussian calculation methods. The orbital energies of different levels of HOMO and LUMO were calculated and the molecular orbital lobe overlapping showed the inter charge transformation between the base molecule and ligand group. From the frontier molecular orbitals (FMO), the possibility of electrophilic and nucleophilic hit also analyzed. The NLO activity of the title compound related to Polarizability and hyperpolarizability were also discussed. The present molecule was fragmented with respect to atomic mass and the mass variation depends on the substitutions have also been studied. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

Calculations of the excitation energies of all-trans and 11,12s-dicis retinals using localized molecular orbitals obtained by the elongation method

Science.gov (United States)

Kurihara, Youji; Aoki, Yuriko; Imamura, Akira

1997-09-01

In the present article, the excitation energies of the all-trans and the 11,12s-dicis retinals were calculated by using the elongation method. The geometries of these molecules were optimized with the 4-31G basis set by using the GAUSSIAN 92 program. The wave functions for the calculation of the excitation energies were obtained with CNDO/S approximation by the elongation method, which enables us to analyze electronic structures of aperiodic polymers in terms of the exciton-type local excitation and the charge transfer-type excitation. The excitation energies were calculated by using the single excitation configuration interaction (SECI) on the basis of localized molecular orbitals (LMOs). The LMOs were obtained in the process of the elongation method. The configuration interaction (CI) matrices were diagonalized by Davidson's method. The calculated results were in good agreement with the experimental data for absorption spectra. In order to consider the isomerization path from 11,12s-dicis to all-trans retinals, the barriers to the rotations about C11-C12 double and C12-C13 single bonds were evaluated.

Tunable Microcavity-Stabilized Quantum Cascade Laser for Mid-IR High-Resolution Spectroscopy and Sensing.

Science.gov (United States)

Borri, Simone; Siciliani de Cumis, Mario; Insero, Giacomo; Bartalini, Saverio; Cancio Pastor, Pablo; Mazzotti, Davide; Galli, Iacopo; Giusfredi, Giovanni; Santambrogio, Gabriele; Savchenkov, Anatoliy; Eliyahu, Danny; Ilchenko, Vladimir; Akikusa, Naota; Matsko, Andrey; Maleki, Lute; De Natale, Paolo

2016-02-17

The need for highly performing and stable methods for mid-IR molecular sensing and metrology pushes towards the development of more and more compact and robust systems. Among the innovative solutions aimed at answering the need for stable mid-IR references are crystalline microresonators, which have recently shown excellent capabilities for frequency stabilization and linewidth narrowing of quantum cascade lasers with compact setups. In this work, we report on the first system for mid-IR high-resolution spectroscopy based on a quantum cascade laser locked to a CaF₂ microresonator. Electronic locking narrows the laser linewidth by one order of magnitude and guarantees good stability over long timescales, allowing, at the same time, an easy way for finely tuning the laser frequency over the molecular absorption line. Improvements in terms of resolution and frequency stability of the source are demonstrated by direct sub-Doppler recording of a molecular line.

Experimental study and nuclear model calculations on the $^{192}Os (p, n)^{192}$Ir reaction Comparison of reactor and cyclotron production of the therapeutic radionuclide $^{192}$Ir

CERN Document Server

Hilgers, K; Sudar, S; 10.1016/j.apradiso.2004.12.010

2005-01-01

In a search for an alternative route of production of the important therapeutic radionuclide /sup 192/Ir (T/sub 1/2/=78.83 d), the excitation function of the reaction /sup 192/Os(p, n)/sup 192/Ir was investigated from its threshold up to 20MeV. Thin samples of enriched /sup 192/Os were obtained by electrodeposition on Ni, and the conventional stacked-foil technique was used for cross section measurements. The experimental data were compared with the results of theoretical calculations using the codes EMPIRE-II and ALICE-IPPE. Good agreement was found with EMPIRE-II, but slightly less with the ALICE-IPPE calculations. The theoretical thick target yield of /sup 192/Ir over the energy range E/sub p/=16 to 8MeV amounts to only 0.16MBq/ mu A.h. A comparison of the reactor and cyclotron production methods is given. In terms of yield and radionuclidic purity of /sup 192/Ir the reactor method appears to be superior; the only advantage of the cyclotron method could be the higher specific activity of the product.

Upconversion excitations in Pr3+-doped BaY2F8 crystal

Science.gov (United States)

Piramidowicz, R.; Mahiou, R.; Boutinaud, P.; Malinowski, M.

2011-09-01

We report the orange-to-blue and infrared-(IR)-to-blue wavelengths upconversion luminescence in Pr3+:BaY2F8 crystals. Mechanism of the orange light upconversion into blue 3P0 state emission was confirmed to be energy transfer between two Pr3+ ions in the 1D2 state. IR-to-blue upconversion has only been observed under two different color IR pumping. The first resonant step was the 3H4→1G4 ground state absorption transition, and the second resonant transition was the excited state absorption from the 1G4 to 1I6 and 3PJ levels. A comparison of the efficiency of the IR-to-blue upconversion in several praseodymium activated host is presented and discussed. A model of the IR pumped upconversion praseodymium blue laser is presented and the population inversion conditions are calculated.

Dynamic modification of the fragmentation of COq+ excited states generated with high-order harmonics

International Nuclear Information System (INIS)

Cao, W.; De, S.; Singh, K. P.; Chen, S.; Laurent, G.; Ray, D.; Ben-Itzhak, I.; Cocke, C. L.; Schoeffler, M. S.; Belkacem, A.; Osipov, T.; Rescigno, T.; Alnaser, A. S.; Bocharova, I. A.; Zherebtsov, S.; Kling, M. F.; Litvinyuk, I. V.

2010-01-01

The dynamic process of fragmentation of CO q+ excited states is investigated using a pump-probe approach. EUV radiation (32-48 eV) generated by high-order harmonics was used to ionize and excite CO molecules and a time-delayed infrared (IR) pulse (800 nm) was used to influence the evolution of the dissociating multichannel wave packet. Two groups of states, separable experimentally by their kinetic-energy release (KER), are populated by the EUV and lead to C + -O + fragmentation: direct double ionization of the neutral molecule and fragmentation of the cation leading to C + -O*, followed by autoionization of O*. The IR pulse was found to modify the KER of the latter group in a delay-dependent way which is explained with a model calculation.

Surface-enhanced Raman scattering (SERS) of riboflavin on nanostructured Ag surfaces: The role of excitation wavelength, plasmon resonance and molecular resonance

Science.gov (United States)

Šubr, Martin; Kuzminova, Anna; Kylián, Ondřej; Procházka, Marek

2018-05-01

Optimization of surface-enhanced Raman scattering (SERS)-based sensors for (bio)analytical applications has received much attention in recent years. For optimum sensitivity, both the nanostructure fabrication process and the choice of the excitation wavelength used with respect to the specific analyte studied are of crucial importance. In this contribution, detailed SERS intensity profiles were measured using gradient nanostructures with the localized surface-plasmon resonance (LSPR) condition varying across the sample length and using riboflavin as the model biomolecule. Three different excitation wavelengths (633 nm, 515 nm and 488 nm) corresponding to non-resonance, pre-resonance and resonance excitation with respect to the studied molecule, respectively, were tested. Results were interpreted in terms of a superposition of the enhancement provided by the electromagnetic mechanism and intrinsic properties of the SERS probe molecule. The first effect was dictated mainly by the degree of spectral overlap between the LSPR band, the excitation wavelength along with the scattering cross-section of the nanostructures, while the latter was influenced by the position of the molecular resonance with respect to the excitation wavelength. Our experimental findings contribute to a better understanding of the SERS enhancement mechanism.

A ROTATING MOLECULAR DISK TOWARD IRAS 18162-2048, THE EXCITING SOURCE OF HH 80-81

International Nuclear Information System (INIS)

Fernandez-Lopez, M.; Curiel, S.; Girart, J. M.; Gomez, Y.; Ho, P. T. P.; Patel, N.

2011-01-01

We present several molecular line emission arcsecond and subarcsecond observations obtained with the Submillimeter Array in the direction of the massive protostar IRAS 18162-2048, the exciting source of HH 80-81. The data clearly indicate the presence of a compact (radius ∼425-850 AU) SO 2 structure, enveloping the more compact (radius ∼ sun . The SO 2 spectral line data also allow us to constrain the structure temperature between 120 and 160 K and the volume density ∼> 2 x 10 9 cm -3 . We also find that such a rotating flattened system could be unstable due to gravitational disturbances. The data from C 17 O line emission show a dense core within this star-forming region. Additionally, the H 2 CO and SO emissions appear clumpy and trace the disk-like structure, a possible interaction between a molecular core and the outflows, and in part, the cavity walls excavated by the thermal radio jet.

FT-IR spectrum of grape seed oil and quantum models of fatty acids triglycerides

Science.gov (United States)

Berezin, K. V.; Antonova, E. M.; Shagautdinova, I. T.; Chernavina, M. L.; Dvoretskiy, K. N.; Grechukhina, O. N.; Vasilyeva, L. M.; Rybakov, A. V.; Likhter, A. M.

2018-04-01

FT-IR spectra of grape seed oil and glycerol were registered in the 650-4000 cm-1 range. Molecular models of glycerol and some fatty acids that compose the oil under study - linoleic, oleic, palmitic and stearic acids - as well as their triglycerides were developed within B3LYP/6-31G(d) density functional model. A vibrating FT-IR spectrum of grape seed oil was modeled on the basis of calculated values of vibrating wave numbers and IR intensities of the fatty acids triglycerides and with regard to their percentage. Triglyceride spectral bands that were formed by glycerol linkage vibrations were revealed. It was identified that triglycerol linkage has a small impact on the structure of fatty acids and, consequently, on vibrating wave numbers. The conducted molecular modeling became a basis for theoretical interpretation on 10 experimentally observed absorption bands in FT-IR spectrum of grape seed oil.

The effect of vibrationally excited nitrogen on the low-latitude ionosphere

Directory of Open Access Journals (Sweden)

B. Jenkins

1997-11-01

Full Text Available The first five vibrationally excited states of molecular nitrogen have been included in the Sheffield University plasmasphere ionosphere model. Vibrationally excited molecular nitrogen reacts much more strongly with atomic oxygen ions than ground-state nitrogen; this means that more O+ ions are converted to NO+ ions, which in turn combine with the electrons to give reduced electron densities. Model calculations have been carried out to investigate the effect of including vibrationally excited molecular nitrogen on the low-latitude ionosphere. In contrast to mid-latitudes, a reduction in electron density is seen in all seasons during solar maximum, the greatest effect being at the location of the equatorial trough.

Two-electron excitation in slow ion-atom collisions: Excitation mechanisms and interferences among autoionizing states

International Nuclear Information System (INIS)

Kimura, M.; Rice Univ., Houston, TX

1990-01-01

The two-electron capture or excitation process resulting from collisions of H + and O 6+ ions with He atoms in the energy range from 0.5 keV/amu to 5 keV/amu is studied within a molecular representation. The collision dynamics for formation of doubly excited O 4+ ions and He** atoms and their (n ell, n'ell ') populations are analyzed in conjunction with electron correlations. Autoionizing states thus formed decay through the Auger process. An experimental study of an ejected electron energy spectrum shows ample structures in addition to two characteristic peaks that are identified by atomic and molecular autoionizations. These structures are attributable to various interferences among electronic states and trajectories. We examine the dominant sources of the interferences. 12 refs., 5 figs

Tunable Microcavity-Stabilized Quantum Cascade Laser for Mid-IR High-Resolution Spectroscopy and Sensing

Directory of Open Access Journals (Sweden)

Simone Borri

2016-02-01

Full Text Available The need for highly performing and stable methods for mid-IR molecular sensing and metrology pushes towards the development of more and more compact and robust systems. Among the innovative solutions aimed at answering the need for stable mid-IR references are crystalline microresonators, which have recently shown excellent capabilities for frequency stabilization and linewidth narrowing of quantum cascade lasers with compact setups. In this work, we report on the first system for mid-IR high-resolution spectroscopy based on a quantum cascade laser locked to a CaF2 microresonator. Electronic locking narrows the laser linewidth by one order of magnitude and guarantees good stability over long timescales, allowing, at the same time, an easy way for finely tuning the laser frequency over the molecular absorption line. Improvements in terms of resolution and frequency stability of the source are demonstrated by direct sub-Doppler recording of a molecular line.

Spectroscopic investigation (FT-IR, FT-Raman), HOMO-LUMO, NBO, and molecular docking analysis of N-ethyl-N-nitrosourea, a potential anticancer agent

Science.gov (United States)

Singh, Priyanka; Islam, S. S.; Ahmad, Hilal; Prabaharan, A.

2018-02-01

Nitrosourea plays an important role in the treatment of cancer. N-ethyl-N-nitrosourea, also known as ENU, (chemical formula C3H7N3O2), is a highly potent mutagen. The chemical is an alkylating agent and acts by transferring the ethyl group of ENU to nucleobases (usually thymine) in nucleic acids. The molecular structure of N-ethyl-N-nitrosourea has been elucidated using experimental (FT-IR and FT-Raman) and theoretical (DFT) techniques. APT charges, Mulliken atomic charges, Natural bond orbital, Electrostatic potential, HOMO-LUMO and AIM analysis were performed to identify the reactive sites and charge transfer interactions. Furthermore, to evaluate the anticancer activity of ENU molecular docking studies were carried out against 2JIU protein.

PACS spectroscopy of OH/IR stars

NARCIS (Netherlands)

Lombaert, R.; de Vries, B.L.; Decin, L.; Blommaert, J.A.D.L.; Royer, Pierre; De Beck, E.; de Koter, A.; Waters, L.B.F.M.

2011-01-01

Observations of high-excitation molecular emission lines can greatly increase our understanding of AGB winds, as they trace the innermost regions of the circumstellar envelope. The PACS spectrometer on-board the Herschel Space Telescope1, provides for the first time the spectral resolution and

4PS/insulin receptor substrate (IRS)-2 is the alternative substrate of the insulin receptor in IRS-1-deficient mice.

Science.gov (United States)

Patti, M E; Sun, X J; Bruening, J C; Araki, E; Lipes, M A; White, M F; Kahn, C R

1995-10-20

Insulin receptor substrate-1 (IRS-1) is the major cytoplasmic substrate of the insulin and insulin-like growth factor (IGF)-1 receptors. Transgenic mice lacking IRS-1 are resistant to insulin and IGF-1, but exhibit significant residual insulin action which corresponds to the presence of an alternative high molecular weight substrate in liver and muscle. Recently, Sun et al. (Sun, X.-J., Wang, L.-M., Zhang, Y., Yenush, L. P., Myers, M. G., Jr., Glasheen, E., Lane, W.S., Pierce, J. H., and White, M. F. (1995) Nature 377, 173-177) purified and cloned 4PS, the major substrate of the IL-4 receptor-associated tyrosine kinase in myeloid cells, which has significant structural similarity to IRS-1. To determine if 4PS is the alternative substrate of the insulin receptor in IRS-1-deficient mice, we performed immunoprecipitation, immunoblotting, and phosphatidylinositol (PI) 3-kinase assays using specific antibodies to 4PS. Following insulin stimulation, 4PS is rapidly phosphorylated in liver and muscle, binds to the p85 subunit of PI 3-kinase, and activates the enzyme. Insulin stimulation also results in the association of 4PS with Grb 2 in both liver and muscle. In IRS-1-deficient mice, both the phosphorylation of 4PS and associated PI 3-kinase activity are enhanced, without an increase in protein expression. Immunodepletion of 4PS from liver and muscle homogenates removes most of the phosphotyrosine-associated PI 3-kinase activity in IRS-1-deficient mice. Thus, 4PS is the primary alternative substrate, i.e. IRS-2, which plays a major role in physiologic insulin signal transduction via both PI 3-kinase activation and Grb 2/Sos association. In IRS-1-deficient mice, 4PS/IRS-2 provides signal transduction to these two major pathways of insulin signaling.

Molecular models of zinc phthalocyanines: semi-empirical molecular orbital computations and physicochemical properties studied by molecular mechanics simulations

International Nuclear Information System (INIS)

Gantchev, Tsvetan G.; van Lier, Johan E.; Hunting, Darel J.

2005-01-01

To build 3D-molecular models of Zinc-phthalocyanines (ZnPc) and to study their diverse chemical and photosensitization properties, we performed quantum mechanical molecular orbital (MO) semi-empirical (AM1) computations of the ground, excited singlet and triplet states as well as free radical (ionic) species. RHF and UHF (open shell) geometry optimizations led to near-perfect symmetrical ZnPc. Predicted ionization potentials (IP), electron affinities (EA) and lowest electronic transitions of ZnPc are in good agreement with the published experimental and theoretical data. The computation-derived D 4h /D 2h -symmetry 3D-structures of ground and excited states and free radicals of ZnPc, together with the frontier orbital energies and Mulliken electron population analysis enabled us to build robust molecular models. These models were used to predict important chemical-reactivity entities such as global electronegativity (χ), hardness (η) and local softness based on Fukui-functions analysis. Examples of molecular mechanics (MM) applications of the 3D-molecular models are presented as approaches to evaluate solvation free energy (ΔG 0 ) solv and to estimate ground- and excited- state oxidation/reduction potentials as well as intermolecular interactions and stability of ground and excited state dimers (exciplexes) and radical ion-pairs

The recombination channels of luminescence excitation in YAG:Yb single crystalline films

International Nuclear Information System (INIS)

Zakharko, Ya.M.; Luchechko, A.P.; Ubizskii, S.B.; Syvorotka, I.I.; Martynyuk, N.V.; Syvorotka, I.M.

2007-01-01

Absorption and emission spectra, luminescence decay kinetics and thermostimulated luminescence of X-ray irradiated YAG:Yb single crystalline films were studied. Two emission bands peaked at 420 and 488 nm have been detected in the investigated films. The strong thermal quenching of luminescence band at 488 nm was observed above 160 K. The influence of growth conditions and annealing in air on the lifetime of Yb 3+ ion excited state in the IR spectral region have been revealed. The recombination mechanisms of the f-f transition at Yb 3+ ion excitation, as well as the mechanism of lifetime shortening for the excited Yb 3+ luminescence have been discussed

Perturbation expansion theory corrected from basis set superposition error. I. Locally projected excited orbitals and single excitations.

Science.gov (United States)

Nagata, Takeshi; Iwata, Suehiro

2004-02-22

The locally projected self-consistent field molecular orbital method for molecular interaction (LP SCF MI) is reformulated for multifragment systems. For the perturbation expansion, two types of the local excited orbitals are defined; one is fully local in the basis set on a fragment, and the other has to be partially delocalized to the basis sets on the other fragments. The perturbation expansion calculations only within single excitations (LP SE MP2) are tested for water dimer, hydrogen fluoride dimer, and colinear symmetric ArM+ Ar (M = Na and K). The calculated binding energies of LP SE MP2 are all close to the corresponding counterpoise corrected SCF binding energy. By adding the single excitations, the deficiency in LP SCF MI is thus removed. The results suggest that the exclusion of the charge-transfer effects in LP SCF MI might indeed be the cause of the underestimation for the binding energy. (c) 2004 American Institute of Physics.

Excitation energy transfer in molecular complexes: transport processes, optical properties and effects of nearby placed metal nano-particles

Science.gov (United States)

May, Volkhard; Megow, Jörg; Zelinskyi, Iaroslav

2012-04-01

Excitation energy transfer (EET) in molecular systems is studied theoretically. Chromophore complexes are considered which are formed by a butanediamine dendrimer with four pheophorbide-a molecules. To achieve a description with an atomic resolution and to account for the effect of an ethanol solvent a mixed quantum classical methodology is utilized. Details of the EET and spectra of transient anisotropy showing signatures of EET are presented. A particular control of intermolecular EET is achieved by surface plasmons of nearby placed metal nanoparticles (MNP). To attain a quantum description of the molecule-MNP system a microscopic theory is introduced. As a particular application surface plasmon affected absorption spectra of molecular complexes placed in the proximity of a spherical MNP are discussed.

Monitoring Voltage-Dependent Charge Displacement of Shaker B-IR K+ Ion Channels Using Radio Frequency Interrogation

OpenAIRE

Dharia, Sameera; Rabbitt, Richard D.

2011-01-01

Here we introduce a new technique that probes voltage-dependent charge displacements of excitable membrane-bound proteins using extracellularly applied radio frequency (RF, 500 kHz) electric fields. Xenopus oocytes were used as a model cell for these experiments, and were injected with cRNA encoding Shaker B-IR (ShB-IR) K(+) ion channels to express large densities of this protein in the oocyte membranes. Two-electrode voltage clamp (TEVC) was applied to command whole-cell membrane potential a...

Alkoholio ir tabako pasiūlos ir paklausos teisinio reguliavimo raida Lietuvos Respublikoje: problemos ir sprendimai

OpenAIRE

Mockevičius, Arminas

2014-01-01

Viešosios teisės magistro studijų programos studento Armino Mockevičiaus buvo parašytas magistro baigiamasis darbas „Alkoholio ir tabako pasiūlos ir paklausos teisinio reguliavimo raida Lietuvos Respublikoje: problemos ir sprendimai“. Šis darbas parašytas Vilniuje, 2014 metais, Mykolo Romerio universiteto Teisės fakulteto Konstitucinės ir administracinės teisės institute, vadovaujant dr. Gintautui Vilkeliui, apimtis 98 p. Darbo tikslas yra atskleisti alkoholio ir tabako pasiūlos ir paklau...

Laser-excited atomic-fluorescence spectrometry with electrothermal tube atomization.

Science.gov (United States)

Vera, J A; Leong, M B; Stevenson, C L; Petrucci, G; Winefordner, J D

1989-12-01

The performance of graphite-tube electrothermal atomizers is evaluated for laser-excited atomic-fluorescence spectrometry for several elements. Three pulsed laser systems are used to pump tunable dye lasers which subsequently are used to excite Pb, Ga, In, Fe, Ir, and Tl atoms in the hot graphite tube. The dye laser systems used are pumped by nitrogen, copper vapour and Nd:YAG lasers. Detection limits in the femtogram and subfemtogram range are typically obtained for all elements. A commercial graphite-tube furnace is important for the successful utilization of the laser-based method when the determination of trace elements is intended, especially when complicated matrices may be present.

Ligand-bridged dinuclear cyclometalated Ir(III) complexes: from metallamacrocycles to discrete dimers.

Science.gov (United States)

Chandrasekhar, Vadapalli; Hajra, Tanima; Bera, Jitendra K; Rahaman, S M Wahidur; Satumtira, Nisa; Elbjeirami, Oussama; Omary, Mohammad A

2012-02-06

Metallamacrocycles 1, 2, and 3 of the general formula [{Ir(ppy)(2)}(2)(μ-BL)(2)](OTf)(2) (ppyH = 2-phenyl pyridine; BL = 1,2-bis(4-pyridyl)ethane (bpa) (1), 1,3-bis(4-pyridyl)propane (bpp) (2), and trans-1,2-bis(4-pyridyl)ethylene (bpe) (3)) have been synthesized by the reaction of [{(ppy)(2)Ir}(2)(μ-Cl)(2)], first with AgOTf to effect dechlorination and later with various bridging ligands. Open-frame dimers [{Ir(ppy)(2)}(2)(μ-BL)](OTf)(2) were obtained in a similar manner by utilizing N,N'-bis(2-pyridyl)methylene-hydrazine (abp) and N,N'-(bis(2-pyridyl)formylidene)ethane-1,2-diamine (bpfd) (for compounds 4 and 5, respectively) as bridging ligands. Molecular structures of 1, 3, 4, and 5 were established by X-ray crystallography. Cyclic voltammetry experiments reveal weakly interacting "Ir(ppy)(2)" units bridged by ethylene-linked bpe ligand in 3; on the contrary the metal centers are electronically isolated in 1 and 2 where the bridging ligands are based on ethane and propane linkers. The dimer 4 exhibits two accessible reversible reduction couples separated by 570 mV indicating the stability of the one-electron reduced species located on the diimine-based bridge abp. The "Ir(ppy)(2)" units in compound 5 are noninteracting as the electronic conduit is truncated by the ethane spacer in the bpfd bridge. The dinuclear compounds 1-5 show ligand centered (LC) transitions involving ppy ligands and mixed metal to ligand/ligand to ligand charge transfer (MLCT/LLCT) transitions involving both the cyclometalating ppy and bridging ligands (BL) in the UV-vis spectra. For the conjugated bridge bpe in compound 3 and abp in compound 4, the lowest-energy charge-transfer absorptions are red-shifted with enhanced intensity. In accordance with their similar electronic structures, compounds 1 and 2 exhibit identical emissions. The presence of vibronic structures in these compounds indicates a predominantly (3)LC excited states. On the contrary, broad and unstructured

Cluster-derived Ir-Sn/SiO2 catalysts for the catalytic dehydrogenation of propane: A spectroscopic study

KAUST Repository

Gallo, Alessandro; Psaro, Rinaldo; Guidotti, Matteo; Dal Santo, Vladimiro; Pergola, Roberto Della; Masih, Dilshad; Izumi, Yasuo

2013-01-01

Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir 4(CO)10(SnCl3)2] and NEt 4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9) 4 onto pre

Electromagnetic radiation of ultrarelativistic particles at scattering in excited medium

International Nuclear Information System (INIS)

Malyshevskij, V.S.

1990-01-01

The interaction between relativistic particles and a gaseous or condensed medium with a high density of nondegenerate excited quantum states involves the coherent conversion of atomic or molecular excitations into electromagnetic radiation

The rotational excitation of HF by H

Science.gov (United States)

Desrousseaux, Benjamin; Lique, François

2018-06-01

The HF molecule is a key tracer of molecular hydrogen in diffuse interstellar medium (ISM). Accurate modelling of the HF abundance in such media requires one to model its excitation by both radiation and collisions. In diffuse ISM, the dominant collisional partners are atomic and molecular hydrogen. We report quantum time-independent calculations of collisional cross-sections and rate coefficients for the rotational excitation of HF by H. The reactive hydrogen exchange channels are taken into account in the scattering calculations. For the first time, HF-H rate coefficients are provided for temperature ranging from 10 to 500 K. The strongest collision-induced rotational HF transitions are those with Δj = 1, and the order of magnitude of the new HF-H rate coefficients is similar to that of the HF-H2 ones previously computed. As a first application, we simulate the excitation of HF by both H and H2 in typical diffuse ISM. We show that, depending on the rotational transition, hydrogen atoms increase or decrease the simulated excitation temperatures compared to collisional excitation only due to H2 molecules. Such results suggest that the new HF-H collisional data have to be used for properly modelling the abundance of HF in diffuse ISM.

Insight into regulation of emission color and photodeactivation process from heteroleptic to homoleptic Ir(III) complexes

Energy Technology Data Exchange (ETDEWEB)

Wang, Xin; Zheng, Danning; Feng, Songyan; Wang, Li, E-mail: chemwangl@henu.edu.cn; Li, Junfeng, E-mail: jfli@theochem.kth.se; Zhang, Jinglai, E-mail: zhangjinglai@henu.edu.cn

2017-03-15

The phosphorescent process of two heteroleptic ((DMDPI){sub 2}Ir(tftap) and (tftap){sub 2}Ir(DMDPI)) and one homoleptic (Ir(DMDPI){sub 3}) Ir(III) complexes (See ) is theoretically investigated by density functional theory (DFT) and quadratic response (QR) time-dependent density functional theory (TDDFT) calculations including spin-orbit coupling (SOC). Two or three triplet excited states are confirmed for three complexes, respectively. On the basis of the respective optimized triplet geometry, the emissive wavelength is determined by the ΔSCF-DFT method. Furthermore, the radiative rate constant (k{sub r}) is also calculated corresponding to each triplet state. Combination of k{sub r} and emissive energy, the emission rule is determined. It is found that complex (DMDPI){sub 2}Ir(tftap) follows the dual emission scenarios, while complexes (tftap){sub 2}Ir(DMDPI) and Ir(DMDPI){sub 3} obey the Kasha rule. The nonradiative rate constant (k{sub nr}) is qualitatively evaluated by the construction of triplet potential surface via metal centered ({sup 3}MC d-d) state. Finally, the sequence of quantum yield is compared by both k{sub r} and k{sub nr}. The quantum yield of homoleptic Ir(III) complex Ir(DMDPI){sub 3} is higher than that of heteroleptic Ir(III) complexes (DMDPI){sub 2}Ir(tftap) and (tftap){sub 2}Ir(DMDPI). However, the emissive wavelength of Ir(DMDPI){sub 3} is in the red color region rather than blue color.

Studies on the substrate mediated vibrational excitation of CO/Si(100) by means of SFG spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Han, Xu; Lass, Kristian; Balgar, Thorsten; Hasselbrink, Eckart [Universitaet Duisburg-Essen, Fachbereich Chemie, 45117 Essen (Germany)

2009-07-01

Vibrational excitations of adsorbates play an important role in chemical reaction dynamics. In the past decade CO on solid surfaces was chosen as adequate model system for studying vibrational relaxation dynamics. Our work is focused on the energy dissipation of vibrationally excited CO adsorbed on a silicon surface by means of IR/Vis sum frequency generation (SFG) spectroscopy. Here we present studies on substrate mediated excitation of vibrational modes of CO on Si(100) induced by UV radiation. We suppose the observation of highly excited internal stretch vibrations of CO caused by hot electrons generated within the silicon substrate.

Atomic collisions research with excited atomic species

International Nuclear Information System (INIS)

Hoogerland, M.D.; Gulley, R.J.; Colla, M.; Lu, W.; Milic, D.; Baldwin, K.G.H.; Buckman, S.J.

1999-01-01

Measurements and calculations of fundamental atomic collision and spectroscopic properties such as collision cross sections, reaction rates, transition probabilities etc. underpin the understanding and operation of many plasma and gas-discharge-based devices and phenomena, for example plasma processing and deposition. In almost all cases the complex series of reactions which sustains the discharge or plasma, or produces the reactive species of interest, has a precursor electron impact excitation, attachment, dissociation or ionisation event. These processes have been extensively studied in a wide range of atomic and molecular species and an impressive data base of collision cross sections and reaction rates now exists. However, most of these measurements are for collisions with stable atomic or molecular species which are initially in their ground electronic state. Relatively little information is available for scattering from excited states or for scattering from unstable molecular radicals. Examples of such species would be metastable excited rare gases, which are often used as buffer gases, or CF 2 radicals formed by electron impact dissociation in a CF 4 plasma processing discharge. We are interested in developing experimental techniques which will enable the quantitative study of such exotic atomic and molecular species. In this talk I would like to outline one such facility which is being used for studies of collisions with metastable He(2 3 S) atoms

Energy relaxation in IR laser excited Hg{sub 1-x}Cd{sub x}Te

Energy Technology Data Exchange (ETDEWEB)

Storebo, A K; Brudevoll, T [FFI - Norwegian Defence Research Establishment, PO Box 25, NO-2027 Kjeller, Norway NTNU (Norwegian University of Science and Technology) (Norway); Olsen, O; Norum, O C [Department of Physics and Department of Electronics and Telecommunications NO-7491 Trondheim (Norway); Breivik, M, E-mail: asta-katrine.storebo@ffi.n [Department of Electronics and Telecommunications NO-7491 Trondheim (Norway)

2009-11-15

IR laser excitation of Hg{sub l-x}Cd{sub x}Te by low-fluence femtosecond and high fluence microsecond pulses was explored for the technologically important alloy fractions x {approx} 0.2 and x {approx} 0.28. We have used first principles (LAPW) electronic structure calculations and finite element modelling, supported by Monte Carlo simulation for the description of femtosecond pulse carrier relaxation and the transport parameters. Laser wavelengths considered were 6.4 - 10.6 {mu}m for x {approx} 0.2 and 3.8 - 4.8 {mu}m for x {approx} 0.28, with an incident 1 microsecond pulse fluence of 2 J/cm{sup 2}. Many energy transfer mechanisms are invoked due to the long timescales of the microsecond pulses, and a main challenge is therefore to elucidate how these interplay in situations away from thermal equilibrium. Mechanisms studied include one- and two-photon absorption (OPA and TPA) across the band gap, inter-valence band absorption (IVA) between light- and heavy hole bands, electron-hole recombination/impact ionization, band gap renormalisation, intra-band free carrier absorption (FCA), excess carrier temperatures, non-equilibrium phonon generation, and refractive index changes. In the high fluence case, lattice temperatures evolve considerably during the laser pulse in response to the heated carriers. The chosen photon energies lie just above the band gap at the starting lattice temperature of 77 K, and nonlinear effects therefore dominate as the material heats up and the band gap begins to exceed the photon energy. Because of the low photon energy we must rely on Auger recombination, inter-valence band absorption and free carrier absorption to heat the carrier plasma. Although some Hg{sub l-x}Cd{sub x}Te material parameters are now relatively well known, existing data for many of the processes are inadequate for cases far away from thermal equilibrium. Furthermore, the role of Auger recombination in relation to non-intrinsic recombination has been a matter of debate

Cooling of molecular ion beams

International Nuclear Information System (INIS)

Wolf, A.; Krohn, S.; Kreckel, H.; Lammich, L.; Lange, M.; Strasser, D.; Grieser, M.; Schwalm, D.; Zajfman, D.

2004-01-01

An overview of the use of stored ion beams and phase space cooling (electron cooling) is given for the field of molecular physics. Emphasis is given to interactions between molecular ions and electrons studied in the electron cooler: dissociative recombination and, for internally excited molecular ions, electron-induced ro-vibrational cooling. Diagnostic methods for the transverse ion beam properties and for the internal excitation of the molecular ions are discussed, and results for phase space cooling and internal (vibrational) cooling are presented for hydrogen molecular ions

Probing Conditions at Ionized/Molecular Gas Interfaces With High Resolution Near-Infrared Spectroscopy

Science.gov (United States)

Kaplan, Kyle Franklin

2017-08-01

Regions of star formation and star death in our Galaxy trace the cycle of gas and dust in the interstellar medium (ISM). Gas in dense molecular clouds collapses to form stars, and stars at the end of their lives return the gas that made up their outer layers back out into the Galaxy. Hot stars generate copious amounts of ultraviolet photons which interact with the surrounding medium and dominate the energetics, ionization state, and chemistry of the gas. The interface where molecular gas is being dissociated into neutral atomic gas by far-UV photons from a nearby hot source is called a photodissociation or photon-dominated region (PDR). PDRs are found primarily in star forming regions where O and B stars serve as the source of UV photons, and in planetary nebulae where the hot core of the dying star acts as the UV source. The main target of this dissertation is molecular hydrogen (H2), the most abundant molecule in the Universe, made from hydrogen formed during the Big Bang. H2 makes up the overwhelming majority of molecules found in the ISM and in PDRs. Far-UV radiation absorbed by H2 will excite an electron in the molecule. The molecule then either dissociates ( 10% of the time; Field et al. 1966) or decays into excited rotational and vibrational ("rovibrational") levels of the electronic ground state. These excited rovibrational levels then decay via a radiative cascade to the ground rovibrational state (v = 0, J = 0), giving rise to a large number of transitions observable in emission from the mid-IR to the optical (Black & van Dishoeck, 1987). These transitions provide an excellent probe of the excitation and conditions within the gas. These transitions are also observed in warm H2, such as in shocks, where collisions excite H2 to higher rovibrational levels. High resolution near-infrared spectroscopy, with its ability to see through dust, and avoid telluric absorption and emission, serves as an effective tool to detect emission from ions, atoms, and molecules

Excited hydrogen bonds in the molecular mechanism of muscle contraction.

Science.gov (United States)

Bespalova, S V; Tolpygo, K B

1991-11-21

The mechanism of muscle contraction is considered. The hydrolysis of an ATP molecule is assumed to produce the excitation of hydrogen bonds A--H...B between electronegative atoms A and B, which are contained in the myosin head and actin filament. This excitation energy epsilon f depends on the interatomic distance AB = R and generates the tractive force f = -delta epsilon f/delta R, that makes atoms AB approach each other. The swing of the myosin head results in macroscopic mutual displacement of actin and myosin polymers. The motion of the actin filament under the action of this force is studied. The conditions under which a considerable portion of the excitation energy converts into the potential tension energy of the actin filament are analysed, and the probability of higher muscle efficiency existence is discussed.

H{sub 2} EXCITATION STRUCTURE ON THE SIGHTLINES TO {delta} SCORPII AND {zeta} OPHIUCI: FIRST RESULTS FROM THE SUB-ORBITAL LOCAL INTERSTELLAR CLOUD EXPERIMENT

Energy Technology Data Exchange (ETDEWEB)

France, Kevin; Nell, Nicholas; Kane, Robert; Green, James C. [Center for Astrophysics and Space Astronomy, University of Colorado, 389 UCB, Boulder, CO 80309 (United States); Burgh, Eric B. [SOFIA/USRA, NASA Ames Research Center, M/S N232-12, Moffett Field, CA 94035 (United States); Beasley, Matthew, E-mail: kevin.france@colorado.edu [Planetary Resources, Inc., 93 S Jackson St 50680, Seattle, WA 98104-2818 (United States)

2013-07-20

We present the first science results from the Sub-orbital Local Interstellar Cloud Experiment (SLICE): moderate resolution 1020-1070 A spectroscopy of four sightlines through the local interstellar medium. High signal-to-noise (S/N) spectra of {eta} Uma, {alpha} Vir, {delta} Sco, and {zeta} Oph were obtained during a 2013 April 21 rocket flight. The SLICE observations constrain the density, molecular photoexcitation rates, and physical conditions present in the interstellar material toward {delta} Sco and {zeta} Oph. Our spectra indicate a factor of two lower total N(H{sub 2}) than previously reported for {delta} Sco, which we attribute to higher S/N and better scattered light control in the new SLICE observations. We find N(H{sub 2}) = 1.5 Multiplication-Sign 10{sup 19} cm{sup -2} on the {delta} Sco sightline, with kinetic and excitation temperatures of 67 and 529 K, respectively, and a cloud density of n{sub H} = 56 cm{sup -3}. Our observations of the bulk of the molecular sightline toward {zeta} Oph are consistent with previous measurements (N(H{sub 2}) Almost-Equal-To 3 Multiplication-Sign 10{sup 20} cm{sup -2} at T{sub 01}(H{sub 2}) = 66 K and T{sub exc} = 350 K). However, we detect significantly more rotationally excited H{sub 2} toward {zeta} Oph than previously observed. We infer a cloud density in the rotationally excited component of n{sub H} Almost-Equal-To 7600 cm{sup -3} and suggest that the increased column densities of excited H{sub 2} are a result of the ongoing interaction between {zeta} Oph and its environment; also manifest as the prominent mid-IR bowshock observed by WISE and the presence of vibrationally excited H{sub 2} molecules observed by the Hubble Space Telescope.

SUPPRESSION OF STAR FORMATION IN THE HOSTS OF LOW-EXCITATION RADIO GALAXIES

Energy Technology Data Exchange (ETDEWEB)

Pace, Cameron; Salim, Samir, E-mail: cameronpace@suu.edu, E-mail: salims@indiana.edu [Indiana University, Department of Astronomy, Swain Hall West 319, Bloomington, IN 47405-7105 (United States)

2016-02-10

The feedback from radio-loud active galactic nuclei (R-AGNs) may help maintain low star-formation (SF) rates in their early-type hosts, but the observational evidence for this mechanism has been inconclusive. We study systematic differences of aggregate spectral energy distributions (SEDs) of various subsets of ∼4000 low-redshift R-AGNs from Best and Heckman with respect to (currently) inactive control samples selected to have matching redshift, stellar mass, population age, axis ratio, and environment. Aggregate SEDs, ranging from the ultraviolet (UV) through mid-infrared (mid-IR, 22 μm), were constructed using a Bayesian method that eliminates biases from non-detections in Galaxy Evolution Explorer and Wide-field Infrared Survey Explorer. We study rare high-excitation sources separately from low-excitation ones, which we split by environment and host properties. We find that both the UV and mid-IR emission of non-cluster R-AGNs (80% of sample) are suppressed by ∼0.2 dex relative to that of the control group, especially for moderately massive galaxies (log M{sub *} ≲ 11). The difference disappears for high-mass R-AGNs and for R-AGNs in clusters, where other, non-AGN quenching/maintenance mechanisms may dominate, or where the suppression of SF due to AGNs may persist between active phases of the central engine, perhaps because of the presence of a hot gaseous halo storing AGN energy. High-excitation (high accretion rate) sources, which make up 2% of the R-AGN sample, do not show any evidence of SF suppression (their UV is the same as in controls), but they exhibit a strong mid-IR excess due to AGN dust heating.

Polarization-Dependent Measurements of Molecular Super Rotors with Oriented Angular Momenta

Science.gov (United States)

Murray, Matthew J.; Toro, Carlos; Liu, Qingnan; Mullin, Amy S.

2014-05-01

Controlling molecular motion would enable manipulation of energy flow between molecules. Here we have used an optical centrifuge to investigate energy transfer between molecular super rotors with oriented angular momenta. The polarizable electron cloud of the molecules interacts with the electric field of linearly polarized light that angularly accelerates over the time of the optical pulse. This process drives molecules into high angular momentum states that are oriented with the optical field and have energies far from equilibrium. High resolution transient IR spectroscopy reveals the dynamics of collisional energy transfer for these super excited rotors. The results of this study leads to a more fundamental understanding of energy balance in non-equilibrium environments and the physical and chemical properties of gases in a new regime of energy states. Results will be presented for several super rotor species including carbon monoxide, carbon dioxide, and acetylene. Polarization-dependent measurements reveal the extent to which the super rotors maintain spatial orientation of high angular momentum states.

DFT Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters

Science.gov (United States)

2017-10-31

VC-nH2O for Small and Water-Dominated Molecular Clusters October 31, 2017 Approved for public release; distribution is unlimited. L. Huang S.g...Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters L. Huang,1 S.G...nH2O molecular clusters using density function theory (DFT). DFT can provide interpretation of absorption spectra with respect to molecular

Photodissociation dynamics of core-excited molecular oxygen

International Nuclear Information System (INIS)

Coutinho, L.H.; Homem, M.G.P.; Marinho, R.R.T.; Mocellin, A.; Naves de Brito, A.; Burmeister, F.

2004-01-01

Full text: The fragmentation of molecules after the excitation of a core orbital is of particular interest due to the localization of these orbitals and the possibility to observe dissociation in the same time scale as the electronic decay. This process, which occurs in a few femtoseconds and is known as ultrafast dissociation, has been observed for O 2 and the results will be presented. We used the PhotoElectron-PhotoIon COincidence (PEPICO) and PhotoElectron-PhotoIon-PhotoIon COincidence (PEPIPICO) spectroscopy technique to analyze the produced fragments in the 529 to 540 eV photon energy range. Usually Electron Spectroscopy (ES) is employed to establish whether this peculiar phenomenon occurs or not. Here we successfully put forward the use of partial ion yield (PIY) spectroscopy to investigate ultrafast dissociation. The experiment was performed at the Brazilian Synchrotron Light Laboratory (LNLS). The SGM beamline was equipped with an end-station composed by a time-of-flight mass spectrometer able to rotate with respect to the polarization of the exciting beam. The measurements were taken with the TOF axis performing an angle of 54.7 deg with respect to the polarization vector of the light. The data were corrected for non-unitary detection efficiency in the detectors

Excited-State Dynamics of a DNA Duplex in a Deep Eutectic Solvent Probed by Femtosecond Time-Resolved IR Spectroscopy.

Science.gov (United States)

de La Harpe, Kimberly; Kohl, Forrest R; Zhang, Yuyuan; Kohler, Bern

2018-03-08

To better understand how the solvent influences excited-state deactivation in DNA strands, femtosecond time-resolved IR (fs-TRIR) pump-probe measurements were performed on a d(AT) 9 ·d(AT) 9 duplex dissolved in a deep eutectic solvent (DES) made from choline chloride and ethylene glycol in a 1:2 mol ratio. This solvent, known as ethaline, is a member of a class of ionic liquids capable of solubilizing DNA with minimal disruption to its secondary structure. UV melting analysis reveals that the duplex studied here melts at 18 °C in ethaline compared to 50 °C in aqueous solution. Ethaline has an excellent transparency window that facilitates TRIR measurements in the double-bond stretching region. Transient spectra recorded in deuterated ethaline at room temperature indicate that photoinduced intrastrand charge transfer occurs from A to T, yielding the same exciplex state previously detected in aqueous solution. This state decays via charge recombination with a lifetime of 380 ± 10 ps compared to the 300 ± 10 ps lifetime measured earlier in D 2 O solution. The TRIR data strongly suggest that the long-lived exciplex forms exclusively in the solvated duplex, and not in the denatured single strands, which appear to have little, if any, base stacking. The longer lifetime of the exciplex state in the DES compared to aqueous solution is suggested to arise from reduced stabilization of the charge transfer state, resulting in slower charge recombination on account of Marcus inverted behavior.

Highly doped InP as a low loss plasmonic material for mid-IR region.

Science.gov (United States)

Panah, M E Aryaee; Takayama, O; Morozov, S V; Kudryavtsev, K E; Semenova, E S; Lavrinenko, A V

2016-12-12

We study plasmonic properties of highly doped InP in the mid-infrared (IR) range. InP was grown by metal-organic vapor phase epitaxy (MOVPE) with the growth conditions optimized to achieve high free electron concentrations by doping with silicon. The permittivity of the grown material was found by fitting the calculated infrared reflectance spectra to the measured ones. The retrieved permittivity was then used to simulate surface plasmon polaritons (SPPs) propagation on flat and structured surfaces, and the simulation results were verified in direct experiments. SPPs at the top and bottom interfaces of the grown epilayer were excited by the prism coupling. A high-index Ge hemispherical prism provides efficient coupling conditions of SPPs on flat surfaces and facilitates acquiring their dispersion diagrams. We observed diffraction into symmetry-prohibited diffraction orders stimulated by the excitation of surface plasmon-polaritons in a periodically structured epilayer. Characterization shows good agreement between the theory and experimental results and confirms that highly doped InP is an effective plasmonic material aiming it for applications in the mid-IR wavelength range.

High-definition Fourier Transform Infrared (FT-IR) Spectroscopic Imaging of Human Tissue Sections towards Improving Pathology

Science.gov (United States)

Nguyen, Peter L.; Davidson, Bennett; Akkina, Sanjeev; Guzman, Grace; Setty, Suman; Kajdacsy-Balla, Andre; Walsh, Michael J.

2015-01-01

High-definition Fourier Transform Infrared (FT-IR) spectroscopic imaging is an emerging approach to obtain detailed images that have associated biochemical information. FT-IR imaging of tissue is based on the principle that different regions of the mid-infrared are absorbed by different chemical bonds (e.g., C=O, C-H, N-H) within cells or tissue that can then be related to the presence and composition of biomolecules (e.g., lipids, DNA, glycogen, protein, collagen). In an FT-IR image, every pixel within the image comprises an entire Infrared (IR) spectrum that can give information on the biochemical status of the cells that can then be exploited for cell-type or disease-type classification. In this paper, we show: how to obtain IR images from human tissues using an FT-IR system, how to modify existing instrumentation to allow for high-definition imaging capabilities, and how to visualize FT-IR images. We then present some applications of FT-IR for pathology using the liver and kidney as examples. FT-IR imaging holds exciting applications in providing a novel route to obtain biochemical information from cells and tissue in an entirely label-free non-perturbing route towards giving new insight into biomolecular changes as part of disease processes. Additionally, this biochemical information can potentially allow for objective and automated analysis of certain aspects of disease diagnosis. PMID:25650759

Characterization of a novel miniaturized burst-mode infrared laser system for IR-MALDESI mass spectrometry imaging.

Science.gov (United States)

Ekelöf, Måns; Manni, Jeffrey; Nazari, Milad; Bokhart, Mark; Muddiman, David C

2018-03-01

Laser systems are widely used in mass spectrometry as sample probes and ionization sources. Mid-infrared lasers are particularly suitable for analysis of high water content samples such as animal and plant tissues, using water as a resonantly excited sacrificial matrix. Commercially available mid-IR lasers have historically been bulky and expensive due to cooling requirements. This work presents a novel air-cooled miniature mid-IR laser with adjustable burst-mode output and details an evaluation of its performance for mass spectrometry imaging. The miniature laser was found capable of generating sufficient energy for complete ablation of animal tissue in the context of an IR-MALDESI experiment with exogenously added ice matrix, yielding several hundred confident metabolite identifications. Graphical abstract The use of a novel miniature 2.94 μm burst-mode laser in IR-MALDESI allows for rapid and sensitive mass spectrometry imaging of a whole mouse.

Localized excitations and the geometry of the 1nπ* excited states of pyrazine

International Nuclear Information System (INIS)

Kleier, D.A.; Martin, R.L.; Wadt, W.R.; Moomaw, W.R.

1982-01-01

Previous theoretical work has shown that the lowest excited singlet state of pyrazine, the π* 1 B 3 u state, is best described in terms of interacting excitations localized on each nitrogen. The present work refines the localized excitation model and considers its implications for the geometry of the 1 B 3 u state. Hartree-Fock calculations show that the best single configuration description of the nπ* state has broken ( 1 B 1 ) symmetry with the excitation strongly localized at one end of the molcule. If the symmetry-restricted hf result is used for reference, this localization describes an important correlation effect. The excited-state geometry was probed using configuration interaction wave functions based on the symmetry-restricted orbitals, as well as properly symmetrized ''valance-bond'' wave functions based on the broken symmetry solutions. Both descriptions lead to a very flat potential for a b/sub 1u/ vibrational mode. This mode reduces the molecular geometry from D/sub 2h/ to C/sub 2v/. We present spectroscopic evidence of our own and of other workers which is consistent with such a flat potential

Direct two-photon excitation of Sm3+, Eu3+, Tb3+, Tb.DOTA-, and Tb.propargylDO3A in solution

Science.gov (United States)

Sørensen, Thomas Just; Blackburn, Octavia A.; Tropiano, Manuel; Faulkner, Stephen

2012-07-01

We have observed direct two-photon excitation of samarium, europium and terbium ions in solution upon near IR excitation using a tuneable pulsed light source, and have also studied two-photon processes in a pair of related terbium complexes, namely [Tb.DOTA]- and Tb.propargylDO3A. Direct two-photon excitation of lanthanides is observed in simple systems in the absence of sensitizing chromophores. Where even simple chromophores such as a triple bond are present in the complex, then single and two-photon excitation of chromophore excited states competes with direct two-photon excitation of the ions and is the dominant pathway for sensitizing formation of the lanthanide excited state.

Mechanism for the Excited-State Multiple Proton Transfer Process of Dihydroxyanthraquinone Chromophores.

Science.gov (United States)

Zhou, Qiao; Du, Can; Yang, Li; Zhao, Meiyu; Dai, Yumei; Song, Peng

2017-06-22

The single and dual cooperated proton transfer dynamic process in the excited state of 1,5-dihydroxyanthraquinone (1,5-DHAQ) was theoretically investigated, taking solvent effects (ethanol) into account. The absorption and fluorescence spectra were simulated, and dual fluorescence exhibited, which is consistent with previous experiments. Analysis of the calculated IR and Raman vibration spectra reveals that the intramolecular hydrogen bonding interactions (O 20 -H 21 ···O 24 and O 22 -H 23 ···O 25 ) are strengthened following the excited proton transfer process. Finally, by constructing the potential energy surfaces of the ground state, first excited singlet state, and triplet state, the mechanism of the intramolecular proton transfer of 1,5-DHAQ can be revealed.

Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions

International Nuclear Information System (INIS)

Carniato, S.; Selles, P.; Andric, L.; Palaudoux, J.; Penent, F.; Lablanquie, P.; Žitnik, M.; Bučar, K.; Nakano, M.; Hikosaka, Y.; Ito, K.

2015-01-01

The formalism developed in the companion Paper I is used here for the interpretation of spectra obtained recently on the nitrogen molecule. Double core-hole ionization K −2 and core ionization-core excitation K −2 V processes have been observed by coincidence electron spectroscopy after ionization by synchrotron radiation at different photon energies. Theoretical and experimental cross sections reported on an absolute scale are in satisfactory agreement. The evolution with photon energy of the relative contribution of shake-up and conjugate shake-up processes is discussed. The first main resonance in the K −2 V spectrum is assigned to a K −2 π ∗ state mainly populated by the 1s→ lowest unoccupied molecular orbital dipolar excitation, as it is in the K −1 V NEXAFS (Near-Edge X-ray Absorption Fine Structure) signals. Closer to the K −2 threshold Rydberg resonances have been also identified, and among them a K −2 σ ∗ resonance characterized by a large amount of 2s/2p hybridization, and double K −2 (2σ ∗ /1π/3σ) −1 1π ∗2 shake-up states. These resonances correspond in NEXAFS spectra to, respectively, the well-known σ ∗ shape resonance and double excitation K −1 (2σ ∗ /1π/3σ) −1 1π ∗2 resonances, all being positioned above the threshold

Characterization of prepared In2O3 thin films: The FT-IR, FT-Raman, UV-Visible investigation and optical analysis.

Science.gov (United States)

Panneerdoss, I Joseph; Jeyakumar, S Johnson; Ramalingam, S; Jothibas, M

2015-08-05

In this original work, the Indium oxide (In2O3) thin film is deposited cleanly on microscope glass substrate at different temperatures by spray pyrolysis technique. The physical properties of the films are characterized by XRD, SEM, AFM and AFM measurements. The spectroscopic investigation has been carried out on the results of FT-IR, FT-Raman and UV-Visible. XRD analysis exposed that the structural transformation of films from stoichiometric to non-stoichiometric orientation of the plane vice versa and also found that, the film is polycrystalline in nature having cubic crystal structure with a preferred grain orientation along (222) plane. SEM and AFM studies revealed that, the film with 0.1M at 500°C has spherical grains with uniform dimension. The complete vibrational analysis has been carried out and the optimized parameters are calculated using HF and DFT (CAM-B3LYP, B3LYP and B3PW91) methods with 3-21G(d,p) basis set. Furthermore, NMR chemical shifts are calculated by using the gauge independent atomic orbital (GIAO) technique. The molecular electronic properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, molecular electrostatic potential energy (MEP) analysis and Polarizability first order hyperpolarizability calculations are performed by time dependent DFT (TD-DFT) approach. The energy excitation on electronic structure is investigated and the assignment of the absorption bands in the electronic spectra of steady compound is discussed. The calculated HOMO and LUMO energies showed the enhancement of energy gap by the addition of substitutions with the base molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) at different temperatures are calculated and interpreted in gas phase. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Nanoparticle Nucleation Is Termolecular in Metal and Involves Hydrogen: Evidence for a Kinetically Effective Nucleus of Three {Ir3H2x·P2W15Nb3O62}6- in Ir(0)n Nanoparticle Formation From [(1,5-COD)IrI·P2W15Nb3O62]8- Plus Dihydrogen.

Science.gov (United States)

Özkar, Saim; Finke, Richard G

2017-04-19

The nucleation process yielding Ir(0) ∼300 nanoparticles from (Bu 4 N) 5 Na 3 [(1,5-COD)Ir·P 2 W 15 Nb 3 O 62 ] (abbreviated hereafter as (COD)Ir·POM 8- , where POM 9- = the polyoxometalate, P 2 W 15 Nb 3 O 62 9- ) under H 2 is investigated to learn the true molecularity, and hence the associated kinetically effective nucleus (KEN), for nanoparticle formation for the first time. Recent work with this prototype transition-metal nanoparticle formation system ( J. Am. Chem. Soc. 2014 , 136 , 17601 - 17615 ) revealed that nucleation in this system is an apparent second-order in the precatalyst, A = (COD)Ir·POM 8- , not the higher order implied by classic nucleation theory and its nA ⇌ A n , "critical nucleus", A n concept. Herein, the three most reasonable more intimate mechanisms of nucleation are tested: bimolecular nucleation, termolecular nucleation, and a mechanism termed "alternative termolecular nucleation" in which 2(COD)Ir + and 1(COD)Ir·POM 8- yield the transition state of the rate-determining step of nucleation. The results obtained definitively rule out a simple bimolecular nucleation mechanism and provide evidence for the alternative termolecular mechanism with a KEN of 3, Ir 3 . All higher molecularity nucleation mechanisms were also ruled out. Further insights into the KEN and its more detailed composition involving hydrogen, {Ir 3 H 2x POM} 6- , are also obtained from the established role of H 2 in the Ir(0) ∼300 formation balanced reaction stoichiometry, from the p(H 2 ) dependence of the kinetics, and from a D 2 /H 2 kinetic isotope effect of 1.2(±0.3). Eight insights and conclusions are presented. A section covering caveats in the current work, and thus needed future studies, is also included.

Laserlike Vibrational Instability in Rectifying Molecular Conductors

DEFF Research Database (Denmark)

Lu, Jing Tao; Hedegård, Per; Brandbyge, Mads

2011-01-01

We study the damping of molecular vibrations due to electron-hole pair excitations in donor-acceptor (D-A) type molecular rectifiers. At finite voltage additional nonequilibrium electron-hole pair excitations involving both electrodes become possible, and contribute to the stimulated emission....... We investigate the effect in realistic molecular rectifier structures using first-principles calculations....

Dynamical analysis of highly excited molecular spectra

Energy Technology Data Exchange (ETDEWEB)

Kellman, M.E. [Univ. of Oregon, Eugene (United States)

1993-12-01

The goal of this program is new methods for analysis of spectra and dynamics of highly excited vibrational states of molecules. In these systems, strong mode coupling and anharmonicity give rise to complicated classical dynamics, and make the simple normal modes analysis unsatisfactory. New methods of spectral analysis, pattern recognition, and assignment are sought using techniques of nonlinear dynamics including bifurcation theory, phase space classification, and quantization of phase space structures. The emphasis is chaotic systems and systems with many degrees of freedom.

Multi-pollutants sensors based on near-IR telecom lasers and mid-IR difference frequency generation: development and applications

International Nuclear Information System (INIS)

Cousin, J.

2006-12-01

At present the detection of VOC and other anthropic trace pollutants is an important challenge in the measurement of air quality. Infrared spectroscopy, allowing spectral regions rich in molecular absorption to be probed, is a suitable technique for in-situ monitoring of the air pollution. Thus the aim of this work was to develop instruments capable of detecting multiple pollutants for in-situ monitoring by IR spectroscopy. A first project benefited from the availability of the telecommunications lasers emitting in near-IR. This instrument was based on an external cavity diode laser (1500 - 1640 nm) in conjunction with a multipass cell (100 m). The detection sensitivity was optimised by employing a balanced detection and a sweep integration procedure. The instrument developed is deployable for in-situ measurements with a sensitivity of -8 cm -1 Hz -1/2 and allowed the quantification of chemical species such as CO 2 , CO, C 2 H 2 , CH 4 and the determination of the isotopic ratio 13 CO 2 / 12 CO 2 in combustion environment The second project consisted in mixing two near-IR fiber lasers in a non-linear crystal (PPLN) in order to produce a laser radiation by difference frequency generation in the middle-IR (3.15 - 3.43 μm), where the absorption bands of the molecules are the most intense. The first studies with this source were carried out on detection of ethylene (C 2 H 4 ) and benzene (C 6 H 6 ). Developments, characterizations and applications of these instruments in the near and middle IR are detailed and the advantages of the 2 spectral ranges is highlighted. (author)

The detectability of cracks using sonic IR

Science.gov (United States)

Morbidini, Marco; Cawley, Peter

2009-05-01

This paper proposes a methodology to study the detectability of fatigue cracks in metals using sonic IR (also known as thermosonics). The method relies on the validation of simple finite-element thermal models of the cracks and specimens in which the thermal loads have been defined by means of a priori measurement of the additional damping introduced in the specimens by each crack. This estimate of crack damping is used in conjunction with a local measurement of the vibration strain during ultrasonic excitation to retrieve the power released at the crack; these functions are then input to the thermal model of the specimens to find the resulting temperature rises (sonic IR signals). The method was validated on mild steel beams with two-dimensional cracks obtained in the low-cycle fatigue regime as well as nickel-based superalloy beams with three-dimensional "thumbnail" cracks generated in the high-cycle fatigue regime. The equivalent 40kHz strain necessary to obtain a desired temperature rise was calculated for cracks in the nickel superalloy set, and the detectability of cracks as a function of length in the range of 1-5mm was discussed.

Effects of Taurine Supplementation on Neuronal Excitability and Glucose Homeostasis.

Science.gov (United States)

El Idrissi, Abdeslem; El Hilali, Fatiha; Rotondo, Salvatore; Sidime, Francoise

2017-01-01

In this study we examined the role of chronic taurine supplementation on plasma glucose homeostasis and brain excitability through activation of the insulin receptor. FVB/NJ male mice were supplemented with taurine in drinking water (0.05% w/v) for 4 weeks and subjected to a glucose tolerance test (7.5 mg/kg BW) after 12 h fasting. We found that taurine-fed mice were slightly hypoglycemic prior to glucose injection and showed significantly reduced plasma glucose at 30 and 60 min post-glucose injection when compared to control mice. Previously, we reported that taurine supplementation induces biochemical changes that target the GABAergic system. Those studies show that taurine-fed mice are hyperexcitable, have reduced GABA A receptors expression and increased GAD and somatostatin expression in the brain. In this study, we found that taurine-fed mice had a significant increase in insulin receptor (IR) immuno-reactivity in the pancreas and all brain regions examined. At the mRNA level, we found that the IR showed differential regional expression. Surprisingly, we found that neurons express the gene for insulin and that taurine had a significant role in regulating insulin gene expression. We propose that increased insulin production and secretion in taurine-fed mice cause an increase activation of the central IR and may be partially responsible for the increased neuronal excitability observed in taurine supplemented mice. Furthermore, the high levels of neuronal insulin expression and its regulation by taurine implicates taurine in the regulation of metabolic homeostasis.

Molecular-dynamics study of the dynamical excitations in commensurate monolayer films of nitrogen molecules on graphite: A test of the corrugation in the nitrogen-graphite potential

DEFF Research Database (Denmark)

Hansen, Flemming Yssing; Bruch, Ludwig Walter

1995-01-01

The dynamical excitations in a commensurate monolayer solid of N2 molecules adsorbed on graphite have been studied using molecular-dynamics simulations. Velocity and rotational correlation functions as well as coherent intermediate scattering functions and dynamical structure factors have been ca...

Power scaling of ultrafast mid-IR source enabled by high-power fiber laser technology

Energy Technology Data Exchange (ETDEWEB)

Zhou, Gengji

2017-11-15

Ultrafast laser sources with high repetition-rate (>10 MHz) and tunable in the mid-infrared (IR) wavelength range of 7-18 μm hold promise for many important spectroscopy applications. Currently, these ultrafast mid- to longwavelength-IR sources can most easily be achieved via difference-frequency generation (DFG) between a pump beam and a signal beam. However, current ultrafast mid- to longwavelength-IR sources feature a low average power, which limits their applications. In this thesis, we propose and demonstrate a novel approach to power scaling of DFG-based ultrafast mid-IR laser sources. The essence of this novel approach is the generation of a high-energy signal beam. Both the pump beam and the signal beam are derived from a home-built Yb-fiber laser system that emits 165-fs pulses centered at 1035 nm with 30-MHz repetition rate and 14.5-W average power (corresponding to 483-nJ pulse energy). We employ fiber-optic self-phase modulation (SPM) to broaden the laser spectrum and generate isolated spectral lobes. Filtering the rightmost spectral lobe leads to femtosecond pulses with >10 nJ pulse energy. Tunable between 1.1-1.2 μm, this SPM-enabled ultrafast source exhibits ∝100 times higher pulse energy than can be obtained from Raman soliton sources in this wavelength range. We use this SPM-enabled source as the signal beam and part of the Yb-fiber laser output as the pump beam. By performing DFG in GaSe crystals, we demonstrate that power scaling of a DFG-based mid-IR source can be efficiently achieved by increasing the signal energy. The resulting mid-IR source is tunable from 7.4 μm to 16.8 μm. Up to 5.04-mW mid-IR pulses centered at 11 μm are achieved. The corresponding pulse energy is 167 pJ, representing nearly one order of magnitude improvement compared with other reported DFG-based mid-IR sources at this wavelength. Despite of low pulse energy, Raman soliton sources have become a popular choice as the signal source. We carry out a detailed study on

Power scaling of ultrafast mid-IR source enabled by high-power fiber laser technology

International Nuclear Information System (INIS)

Zhou, Gengji

2017-11-01

Ultrafast laser sources with high repetition-rate (>10 MHz) and tunable in the mid-infrared (IR) wavelength range of 7-18 μm hold promise for many important spectroscopy applications. Currently, these ultrafast mid- to longwavelength-IR sources can most easily be achieved via difference-frequency generation (DFG) between a pump beam and a signal beam. However, current ultrafast mid- to longwavelength-IR sources feature a low average power, which limits their applications. In this thesis, we propose and demonstrate a novel approach to power scaling of DFG-based ultrafast mid-IR laser sources. The essence of this novel approach is the generation of a high-energy signal beam. Both the pump beam and the signal beam are derived from a home-built Yb-fiber laser system that emits 165-fs pulses centered at 1035 nm with 30-MHz repetition rate and 14.5-W average power (corresponding to 483-nJ pulse energy). We employ fiber-optic self-phase modulation (SPM) to broaden the laser spectrum and generate isolated spectral lobes. Filtering the rightmost spectral lobe leads to femtosecond pulses with >10 nJ pulse energy. Tunable between 1.1-1.2 μm, this SPM-enabled ultrafast source exhibits ∝100 times higher pulse energy than can be obtained from Raman soliton sources in this wavelength range. We use this SPM-enabled source as the signal beam and part of the Yb-fiber laser output as the pump beam. By performing DFG in GaSe crystals, we demonstrate that power scaling of a DFG-based mid-IR source can be efficiently achieved by increasing the signal energy. The resulting mid-IR source is tunable from 7.4 μm to 16.8 μm. Up to 5.04-mW mid-IR pulses centered at 11 μm are achieved. The corresponding pulse energy is 167 pJ, representing nearly one order of magnitude improvement compared with other reported DFG-based mid-IR sources at this wavelength. Despite of low pulse energy, Raman soliton sources have become a popular choice as the signal source. We carry out a detailed study on

Cometary models - excitation of molecules at radio wavelengths and thermodynamics of the coma

International Nuclear Information System (INIS)

Crovisier, J.

1987-01-01

Models for molecular excitation under physical conditions of cometary atmospheres are obviously a requisite for interpreting radio spectroscopic observations of comets. A review of such models is presented. The prevailing excitation mechanism for the rotational lines of parent molecules is pumping of the fundamental vibrational bands by the solar infrared radiation field, followed by spontaneous decay; the molecular rotational population is then at fluorescence equilibrium. Another competing mechanism in the inner coma is thermal excitation by collisions. Its evaluation needs the knowledge of the coma kinetic temperature law, which up to now can only be achieved by modeling the coma thermodynamics. A review of cometary thermodynamical models is also given here, and the relations between such models and cometary molecular observations are discussed. 50 references

Phase-Sensitive Control Of Molecular Dissociation Through Attosecond Pump/Strong-Field Mid-IR Probe Spectroscopy

Science.gov (United States)

2016-04-15

splitter (consisting of a thin, uncoated, silicon plate at brewsters angle) and the beams were focused onto the OPA crystal. For this work two...experiments in the future. These technologies include • Two-color driven (EUV/mid-IR) ion spectroscopy: we designed an interferometer combining EUV...isolated single-femtosecond EUV pulse generation: combining the use of low ionization threshold gas, an annual near-IR drive beam , polarization

Synthesis and photophysical studies of blue phosphorescent Ir(III) complexes with dimethylphenylphospine.

Science.gov (United States)

Ham, Ho-Wan; Jung, Kyung-Yoon; Kim, Young-Sik

2012-02-01

New blue emitting mixed ligand iridium(III) complexes comprising one cyclometalating, two phosphines trans to each other such as Ir{(CF3)2Meppy}(PPhMe3)2(H)(L) [L = CI, NCMe, CN] [(CF3)2Meppy = 2-(3', 5'-bis-trifluoromethylphenyl)-4-methylpyridine] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. To achieve deep blue emission, the trifluoromethyl group substituted on the phenyl ring and the methyl group substituted on the pyridyl ring increased HOMO-LUMO gap and achieved the hypsochromic shift. To gain insight into the factors responsible for the emission color change and the different luminescence efficiency, we investigate the electron-withdrawing capabilities of ancillary ligands using the DFT and TD-DFT calculations on the ground and excited states of the complexes. From these results, we discuss how the ancillary ligand influences the emission peak as well as the metal to ligand charge transfer (MLCT) transition efficiency. The maximum emission spectra of Ir{(CF3)2Meppy}(PPhMe3)2(H)(Cl), [Ir{(CF3),Meppy)(PPhMe3),(H)(NCMe)]+ and Ir{(CF3)2Meppy}(PPhMe3)2(H)(CN) were in the ranges of 441, 435, 434 nm, respectively.

Watson-Crick base pairing controls excited-state decay in natural DNA.

Science.gov (United States)

Bucher, Dominik B; Schlueter, Alexander; Carell, Thomas; Zinth, Wolfgang

2014-10-13

Excited-state dynamics are essential to understanding the formation of DNA lesions induced by UV light. By using femtosecond IR spectroscopy, it was possible to determine the lifetimes of the excited states of all four bases in the double-stranded environment of natural DNA. After UV excitation of the DNA duplex, we detected a concerted decay of base pairs connected by Watson-Crick hydrogen bonds. A comparison of single- and double-stranded DNA showed that the reactive charge-transfer states formed in the single strands are suppressed by base pairing in the duplex. The strong influence of the Watson-Crick hydrogen bonds indicates that proton transfer opens an efficient decay path in the duplex that prohibits the formation or reduces the lifetime of reactive charge-transfer states. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New infrared observations of IRS 1, IRS 3, and the adjacent nebula in the OMC-2 cluster

International Nuclear Information System (INIS)

Pendelton, Y.; Werner, M.; Dinerstein, H.

1984-01-01

Recent reports show that near infrared reflection nebulae are often observed around embedded protostellar objects. New observations are here reported of the infrared cluster of low luminosity protostars in Orion Molecular Cloud 2 (OMC2). It has been determined that the asymmetric distribution of the extended emission seen about IRS1 is in fact another infrared reflection nebula. Observations of near infrared polarimetry, photometry, and spectrophotometry were carried out at the NASA Infrared Telescope Facility October 1982 and January 1983. (author)

Ab initio R-matrix/Multi-channel Quantum Defect Theory applied to Molecular Core Excitation and Ionization

International Nuclear Information System (INIS)

Hiyama, M.; Kosugi, N.

2004-01-01

Full text: Ab initio R-matrix/MQDT approach, which is a combination of ab initio R-matrix techniques and the multi channel quantum defect theory (MQDT), has recently been developed by one of the present authors (MH) and Child, to successfully obtain the potential energy curves of Rydberg states converging to not only the lowest but also the higher ionized states. This approach is also applied to estimate the valence state interaction with Rydberg and continuum (ionization) channels. Very recently we have made an original ab initio polyatomic R-matrix/MQDT program package, GSCF4R based on Gaussian type basis functions for the bound and continuum states, to extensively study molecular excitation and ionization in the X-ray region as well as in the VUV region. We are going to report the results for core excitation and ionization of diatomic molecules such as NO and O 2 to show that the R-matrix/MQDT method is indispensable to describe the core-to-Rydberg states with the higher quantum number and the continuum states. These results lead us to the conclusion that the close-coupling approximation augmented with the correlation term within the R-matrix/MQDT formalism is powerful to calculate the Rydberg-valence mixing and the interchannel coupling between several core-ionized states

In situ detection of atomic and molecular iodine using Resonance and Off-Resonance Fluorescence by Lamp Excitation: ROFLEX

Directory of Open Access Journals (Sweden)

J. C. Gómez Martín

2011-01-01

Full Text Available We demonstrate a new instrument for in situ detection of atmospheric iodine atoms and molecules based on atomic and molecular resonance and off-resonance ultraviolet fluorescence excited by lamp emission. The instrument combines the robustness, light weight, low power consumption and efficient excitation of radio-frequency discharge light sources with the high sensitivity of the photon counting technique. Calibration of I₂ fluorescence is achieved via quantitative detection of the molecule by Incoherent Broad Band Cavity-enhanced Absorption Spectroscopy. Atomic iodine fluorescence signal is calibrated by controlled broad band photolysis of known I₂ concentrations in the visible spectral range at atmospheric pressure. The instrument has been optimised in laboratory experiments to reach detection limits of 1.2 pptv for I atoms and 13 pptv for I₂, for S/N = 1 and 10 min of integration time. The ROFLEX system has been deployed in a field campaign in northern Spain, representing the first concurrent observation of ambient mixing ratios of iodine atoms and molecules in the 1–350 pptv range.

Experimental bandstructure of the 5 d transition metal oxide IrO2

Science.gov (United States)

Kawasaki, Jason; Nie, Yuefeng; Uchida, Masaki; Schlom, Darrell; Shen, Kyle

2015-03-01

In the 5 d iridium oxides the close energy scales of spin-orbit coupling and electron-electron correlations lead to emergent quantum phenomena. Much research has focused on the ternary iridium oxides, e.g. the Ruddlesden-Poppers An + 1BnO3 n + 1 , which exhibit behavior from metal to antiferromagnetic insulator ground states, share common features with the cuprates, and may host a number of topological phases. The binary rutile IrO2 is another important 5 d oxide, which has technological importance for spintronics due to its large spin Hall effect and also applications in catalysis. IrO2 is expected to share similar physics as its perovskite-based cousins; however, due to bond-length distortions of the IrO6 octahedra in the rutile structure, the extent of similarities remains an open question. Here we use angle-resolved photoemission spectroscopy to perform momentum-resolved measurements of the electronic structure of IrO2 . IrO2 thin films were grown by molecular beam epitaxy on TiO2 (110) substrates using an Ir e-beam source and distilled ozone. Films were subsequently transferred through ultrahigh vacuum to a connected ARPES system. Combined with first-principles calculations we explore the interplay of spin-orbit coupling and correlations in IrO2 .

α-Lipoic acid stabilized DTX/IR780 micelles for photoacoustic/fluorescence imaging guided photothermal therapy/chemotherapy of breast cancer.

Science.gov (United States)

Li, WenTing; Peng, JinRong; Yang, Qian; Chen, LiJuan; Zhang, Lan; Chen, XiaoXin; Qian, ZhiYong

2018-05-01

Micellar nanoparticles have unique advantages as carriers for therapeutic or imaging agents, owing to their smaller size and better penetration of tumors. However, some agents, due to their physical or chemical properties, are difficult to load into micelles. IR780 is one of these agents, and is also a promising near-infrared dye for fluorescence imaging (FI)/photoacoustic imaging (PAI) and cancer photothermal therapy (PTT). Its hydrophobic and high crystallization structure results in limited bioavailability in vivo. It is difficult to load into micelles constructed from an amphiphilic block polymer with relatively low molecular weight. In this study, we use computer simulation and introduce another small biomolecule, α-lipoic acid, into the micelles constructed from a mPEG-PCL copolymer, to lower the energy of molecular interaction between MPEG-PCL and IR780, and expect to enhance the loading capacity of the micelles to IR780. The introduction of α-lipoic acid decreases the energy of molecular interaction between MEPG-PCL and IR780 from -46.18 kJ mol-1 to -196.52 kJ mol-1 and increases the loading capacity and stability of the mPEG-PCL micelles to IR780, which also maintains the loading capacity to DTX. We further construct DTX/IR780 co-loaded mPEG-PCL micelles for FI/PAI dual modal imaging guided PTT/chemotherapy of cancer. By FI and PAI evaluation in vitro and in vivo, we demonstrate that the DTX/IR780 co-loaded micelles can be used as FI and PAI probes. By further evaluating the therapeutic outcome of PTT/chemotherapy co-therapy of breast cancer, we demonstrate that the DTX/IR780 co-loaded mPEG-PCL micelles can serve as promising candidates for FI and PAI guided PTT/chemotherapy of breast cancer.

Room-temperature atomic layer deposition of ZrO{sub 2} using tetrakis(ethylmethylamino)zirconium and plasma-excited humidified argon

Energy Technology Data Exchange (ETDEWEB)

Kanomata, K. [Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510 (Japan); Japan Society for the Promotion of Science, 5-3-1 Kojimachi, Chiyoda-ku, Tokyo 102-0083 (Japan); Tokoro, K.; Imai, T.; Pansila, P.; Miura, M.; Ahmmad, B.; Kubota, S.; Hirahara, K. [Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510 (Japan); Hirose, F., E-mail: fhirose@yz.yamagata-u.ac.jp [Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510 (Japan)

2016-11-30

Highlights: • RT-ALD of ZrO{sub 2} is developed using TEMAZ and plasma-excited humidified argon. • The plasma-excited humidified argon is effective in oxidizing the TEMAZ saturated ZrO{sub 2}. • We discuss the reaction mechanism of the RT-ZrO{sub 2} ALD. - Abstract: Room-temperature atomic layer deposition (ALD) of ZrO{sub 2} is developed with tetrakis(ethylmethylamino)zirconium (TEMAZ) and a plasma-excited humidified argon. A growth per cycle of 0.17 nm/cycle at room temperature is confirmed, and the TEMAZ adsorption and its oxidization on ZrO{sub 2} are characterized by IR absorption spectroscopy with a multiple internal reflection mode. TEMAZ is saturated on a ZrO{sub 2} surface with exposures exceeding ∼2.0 × 10{sup 5} Langmuir (1 Langmuir = 1.0 × 10{sup −6} Torr s) at room temperature, and the plasma-excited humidified argon is effective in oxidizing the TEMAZ-adsorbed ZrO{sub 2} surface. The IR absorption spectroscopy suggests that Zr-OH works as an adsorption site for TEMAZ. The reaction mechanism of room-temperature ZrO{sub 2} ALD is discussed in this paper.

Ultrafast molecular dynamics illuminated with synchrotron radiation

International Nuclear Information System (INIS)

Bozek, John D.; Miron, Catalin

2015-01-01

Highlights: • Ultrafast molecular dynamics probed with synchrotron radiation. • Core-excitation as probe of ultrafast dynamics through core-hole lifetime. • Review of experimental and theoretical methods in ultrafast dynamics using core-level excitation. - Abstract: Synchrotron radiation is a powerful tool for studying molecular dynamics in small molecules in spite of the absence of natural matching between the X-ray pulse duration and the time scale of nuclear motion. Promoting core level electrons to unoccupied molecular orbitals simultaneously initiates two ultrafast processes, nuclear dynamics on the potential energy surfaces of the highly excited neutral intermediate state of the molecule on the one hand and an ultrafast electronic decay of the intermediate excited state to a cationic final state, characterized by a core hole lifetime. The similar time scales of these processes enable core excited pump-probe-type experiments to be performed with long duration X-ray pulses from a synchrotron source. Recent results obtained at the PLIEADES beamline concerning ultrafast dissociation of core excited states and molecular potential energy curve mapping facilitated by changes in the geometry of the short-lived intermediate core excited state are reviewed. High brightness X-ray beams combined with state-of-the art electron and ion-electron coincidence spectrometers and highly sophisticated theoretical methods are required to conduct these experiments and to achieve a full understanding of the experimental results.

The TApIR experiment. IR absorption spectra of liquid hydrogen isotopologues; Das TApIR Experiment IR-Absorptionsspektren fluessiger Wasserstoffisotopologe

Energy Technology Data Exchange (ETDEWEB)

Groessle, Robin

2015-11-27

The scope of the thesis is the infrared absorption spectroscopy of liquid hydrogen isotopologues with the tritium absorption infrared spectroscopy (TApIR) experiment at the tritium laboratory Karlsruhe (TLK). The calibration process from the sample preparation to the reference measurements are described. A further issue is the classical evaluation of FTIR absorption spectra and the extension using the rolling circle filter (RCF) including the effects on statistical and systematical errors. The impact of thermal and nuclear spin temperature on the IR absorption spectra is discussed. An empirical based modeling for the IR absorption spectra of liquid hydrogen isotopologues is performed.

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

Science.gov (United States)

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

2013-01-02

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

Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

Science.gov (United States)

Oh, Juwon; Sung, Young Mo; Hong, Yongseok; Kim, Dongho

2018-03-06

Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To

Tidal Distortion of the Envelope of an AGB Star IRS 3 near Sgr A{sup *}

Energy Technology Data Exchange (ETDEWEB)

Yusef-Zadeh, F.; Royster, M. J.; Roberts, D. A. [Department of Physics and Astronomy, Northwestern University, Evanston, IL 60208 (United States); Wardle, M. [Department of Physics and Astronomy and Research Center for Astronomy, Astrophysics and Astrophotonics, Macquarie University, Sydney NSW 2109 (Australia); Cotton, W.; Kunneriath, D. [National Radio Astronomy Observatory, Charlottesville, VA 22903 (United States); Schödel, R. [Instituto de Astfisica de Andalucia (CSIC), Glorieta de la Astronomia S/N, E-18008 Granada (Spain)

2017-03-01

We present radio and millimeter continuum observations of the Galactic center taken with the Very Large Array (VLA) and ALMA at 44 and 226 GHz, respectively. We detect radio and millimeter emission from IRS 3, lying ∼4.″5 NW of Sgr A*, with a spectrum that is consistent with the photospheric emission from an AGB star at the Galactic center. Millimeter images reveal that the envelope of IRS 3, the brightest and most extended 3.8 μ m Galactic center stellar source, consists of two semicircular dust shells facing the direction of Sgr A*. The outer circumstellar shell, at a distance of 1.6 × 10{sup 4} au, appears to break up into “fingers” of dust directed toward Sgr A*. These features coincide with molecular CS (5–4) emission and a near-IR extinction cloud distributed between IRS 3 and Sgr A*. The NE–SW asymmetric shapes of the IRS 3 shells seen at 3.8 μ m and radio are interpreted as structures that are tidally distorted by Sgr A*. Using the kinematics of CS emission and the proper motion of IRS 3, the tidally distorted outflowing material from the envelope after 5000 yr constrains the distance of IRS 3 to ∼0.7 pc in front of or ∼0.5 pc behind Sgr A*. This suggests that the mass loss by stars near Sgr A* can supply a reservoir of molecular material near Sgr A*. We also present dark features in radio continuum images coincident with the envelope of IRS 3. These dusty stars provide examples in which high-resolution radio continuum images can identify dust-enshrouded stellar sources embedded in an ionized medium.

Design considerations for highly effective fluorescence excitation and detection optical systems for molecular diagnostics

Science.gov (United States)

Kasper, Axel; Van Hille, Herbert; Kuk, Sola

2018-02-01

Modern instruments for molecular diagnostics are continuously optimized for diagnostic accuracy, versatility and throughput. The latest progress in LED technology together with tailored optics solutions allows developing highly efficient photonics engines perfectly adapted to the sample under test. Super-bright chip-on-board LED light sources are a key component for such instruments providing maximum luminous intensities in a multitude of narrow spectral bands. In particular the combination of white LEDs with other narrow band LEDs allows achieving optimum efficiency outperforming traditional Xenon light sources in terms of energy consumption, heat dissipation in the system, and switching time between spectral channels. Maximum sensitivity of the diagnostic system can only be achieved with an optimized optics system for the illumination and imaging of the sample. The illumination beam path must be designed for optimum homogeneity across the field while precisely limiting the angular distribution of the excitation light. This is a necessity for avoiding spill-over to the detection beam path and guaranteeing the efficiency of the spectral filtering. The imaging optics must combine high spatial resolution, high light collection efficiency and optimized suppression of excitation light for good signal-to-noise ratio. In order to achieve minimum cross-talk between individual wells in the sample, the optics design must also consider the generation of stray light and the formation of ghost images. We discuss what parameters and limitations have to be considered in an integrated system design approach covering the full path from the light source to the detector.

Mixed quantum-classical molecular dynamics study of the hydroxyl stretch in methanol/carbon-tetrachloride mixtures II: excited state hydrogen bonding structure and dynamics, infrared emission spectrum, and excited state lifetime.

Science.gov (United States)

Kwac, Kijeong; Geva, Eitan

2012-03-08

We present a mixed quantum-classical molecular dynamics study of the hydrogen-bonding structure and dynamics of a vibrationally excited hydroxyl stretch in methanol/carbon-tetrachloride mixtures. The adiabatic Hamiltonian of the quantum-mechanical hydroxyl is diagonalized on-the-fly to obtain the ground and first-excited adiabatic energy levels and wave functions which depend parametrically on the instantaneous configuration of the classical degrees of freedom. The dynamics of the classical degrees of freedom are determined by Hellmann-Feynman forces obtained by taking the expectation value of the force with respect to the ground or excited vibrational wave functions. Polarizable force fields are used which were previously shown to reproduce the experimental infrared absorption spectrum rather well, for different isotopomers and over a wide composition range [Kwac, K.; Geva, E. J. Phys. Chem. B 2011, 115, 9184]. We show that the agreement of the absorption spectra with experiment can be further improved by accounting for the dependence of the dipole moment derivatives on the configuration of the classical degrees of freedom. We find that the propensity of a methanol molecule to form hydrogen bonds increases upon photoexcitation of its hydroxyl stretch, thereby leading to a sizable red-shift of the corresponding emission spectrum relative to the absorption spectrum. Treating the relaxation from the first excited to the ground state as a nonadiabatic process, and calculating its rate within the framework of Fermi's golden rule and the harmonic-Schofield quantum correction factor, we were able to predict a lifetime which is of the same order of magnitude as the experimental value. The experimental dependence of the lifetime on the transition frequency is also reproduced. Nonlinear mapping relations between the hydroxyl transition frequency and bond length in the excited state and the electric field along the hydroxyl bond axis are established. These mapping relations

Tarptautinio turizmo raida ir vystymo prognozės Lietuvoje ir Lenkijoje

OpenAIRE

Veličkaitė, Dalia

2009-01-01

Išanalizuota ir įvertinta Lietuvos ir Lenkijos atvykstamojo turizmo raida 2000- 2007m., užsienio turistų srautai, apgyvendinimo paslaugų paklausa, turistų tikslai ir kelionių transporto pasirinkimas, turistų išlaidos ir šalių turizmo pajamos, iškeltos atvykstamojo turizmo problemos bei pateikti jų sprendimo siūlymai.paskutinėje darbo dalyje buvo atliktos 2008- 2015metų Lietuvos ir Lenkijos turizmo raidos prognozės. In the final master work Lithuanian and Poland arriving tourism development...

High spin states in 181Ir and backbending phenomena in the Os-Pt region

Science.gov (United States)

Kaczarowski, R.; Garg, U.; Funk, E. G.; Mihelich, J. W.

1992-01-01

The 169Tm(16O,4n)181Ir reaction has been employed to investigate the high spin states of 181Ir using in-beam γ spectroscopy. A well-developed system of levels built on the h9/2 subshell was identified up to a maximum spin of (41/2-). Two rotational bands built on the isomeric states with τ1/2=0.33 μs (Ex=289.2 keV) and 0.13 μs (Ex=366.2 keV), respectively, were observed. The deduced gK values of 1.19+/-0.11 and 1.50+/-0.12 indicate Nilsson assignments of 9/2-[514] and 5/2+[402], respectively, for the bandheads of these bands. A high spin (I>=19/2) isomer with τ1/2=22 ns was found at an excitation energy above 1.96 MeV. The experimental results are discussed in terms of rotational models including Coriolis coupling and providing for a stable triaxial shape of the 181Ir nucleus.

Direct Determination of Molecular Weight Distribution of Calf-Thymus DNAs and Study of Their Fragmentation under Ultrasonic and Low-Energy IR Irradiations. A Charge Detection Mass Spectrometry Investigation.

Science.gov (United States)

Halim, Mohammad A; Bertorelle, Franck; Doussineau, Tristan; Antoine, Rodolphe

2018-06-09

Calf-thymus (CT-DNA) is widely used as binding agent. The commercial samples are known to be "highly polymerized DNA" samples. CT-DNA is known to be fragile in particular upon ultrasonic wave irradiation. Degradation products might have dramatic consequence on its bio-sensing activity, and an accurate determination of the molecular weight distribution and stability of commercial samples is highly demanded. We investigated the sensitivity of charge detection mass spectrometry (CDMS), a single-molecule MS method, both with single-pass and ion trap CDMS ("Benner" trap) modes to the determination of the composition and stability (under multiphoton IR irradiation) of calf-thymus DNAs. We also investigated the changes of molecular weight distributions in the course of sonication by irradiating ultrasonic wave to CT-DNA. We report for the first time, the direct molecular weight (MW) distribution of DNA sodium salt from calf-thymus revealing two populations at high (~10 MDa) and low (~3 MDa) molecular weights. We evidence a transition between the high-MW to the low-MW distribution, confirming that the low-MW distribution results from degradation of CT-DNA. Finally, we report also IRMPD experiments carried out on trapped single-stranded linear DNAs from calf-thymus allowing to extract their activation energy for unimolecular dissociation. We show that single-pass CDMS is a direct, efficient and accurate MS-based approach to determine the composition of calf-thymus DNAs. Furthermore, ion trap CDMS allows us to evaluate the stability (both under multiphoton IR irradiation and in the course of sonication by irradiating ultrasonic wave) of calf-thymus DNAs. This article is protected by copyright. All rights reserved.

The dynamics of molecular dimers in the crystals of m-aminobenzoic acid studied by inelastic neutron scattering (INS), Raman, IR spectroscopy and DFT calculations

Energy Technology Data Exchange (ETDEWEB)

Pawlukojc, A.; Leciejewicz, J

2004-03-29

Inelastic neutron scattering, Raman and IR spectra were measured for m-aminobenzoic acid (MABA). Optimized geometries and observed frequencies were assigned using DFT calculation on the B3LYP/6-311G** level using Gaussian 98 and Gamess programs. Experimental structural and spectroscopic data are in good agreement with computations assuming the presence in the crystals of molecular dimers composed of two MABA molecules linked by a pair of O-H...O hydrogen bonds each provided by the carboxylic group. INS frequencies have been identified for the O-H (out of plane) mod0008.

Electronic structure, local magnetism, and spin-orbit effects of Ir(IV)-, Ir(V)-, and Ir(VI)-based compounds

Energy Technology Data Exchange (ETDEWEB)

Laguna-Marco, M. A.; Kayser, P.; Alonso, J. A.; Martínez-Lope, M. J.; van Veenendaal, M.; Choi, Y.; Haskel, D.

2015-06-01

Element- and orbital-selective x-ray absorption and magnetic circular dichroism measurements are carried out to probe the electronic structure and magnetism of Ir 5d electronic states in double perovskite Sr2MIrO6 (M = Mg, Ca, Sc, Ti, Ni, Fe, Zn, In) and La2NiIrO6 compounds. All the studied systems present a significant influence of spin-orbit interactions in the electronic ground state. In addition, we find that the Ir 5d local magnetic moment shows different character depending on the oxidation state despite the net magnetization being similar for all the compounds. Ir carries an orbital contribution comparable to the spin contribution for Ir4+ (5d(5)) and Ir5+ (5d(4)) oxides, whereas the orbital contribution is quenched for Ir6+ (5d(3)) samples. Incorporation of a magnetic 3d atom allows getting insight into the magnetic coupling between 5d and 3d transition metals. Together with previous susceptibility and neutron diffractionmeasurements, the results indicate that Ir carries a significant local magnetic moment even in samples without a 3d metal. The size of the (small) net magnetization of these compounds is a result of predominant antiferromagnetic interactions between local moments coupled with structural details of each perovskite structure

IR-IR Conformation Specific Spectroscopy of Na+(Glucose) Adducts

Science.gov (United States)

Voss, Jonathan M.; Kregel, Steven J.; Fischer, Kaitlyn C.; Garand, Etienne

2018-01-01

We report an IR-IR double resonance study of the structural landscape present in the Na+(glucose) complex. Our experimental approach involves minimal modifications to a typical IR predissociation setup, and can be carried out via ion-dip or isomer-burning methods, providing additional flexibility to suit different experimental needs. In the current study, the single-laser IR predissociation spectrum of Na+(glucose), which clearly indicates contributions from multiple structures, was experimentally disentangled to reveal the presence of three α-conformers and five β-conformers. Comparisons with calculations show that these eight conformations correspond to the lowest energy gas-phase structures with distinctive Na+ coordination. [Figure not available: see fulltext.

PKCδ-mediated IRS-1 Ser24 phosphorylation negatively regulates IRS-1 function

International Nuclear Information System (INIS)

Greene, Michael W.; Ruhoff, Mary S.; Roth, Richard A.; Kim, Jeong-a; Quon, Michael J.; Krause, Jean A.

2006-01-01

The IRS-1 PH and PTB domains are essential for insulin-stimulated IRS-1 Tyr phosphorylation and insulin signaling, while Ser/Thr phosphorylation of IRS-1 disrupts these signaling events. To investigate consensus PKC phosphorylation sites in the PH-PTB domains of human IRS-1, we changed Ser24, Ser58, and Thr191 to Ala (3A) or Glu (3E), to block or mimic phosphorylation, respectively. The 3A mutant abrogated the inhibitory effect of PKCδ on insulin-stimulated IRS-1 Tyr phosphorylation, while reductions in insulin-stimulated IRS-1 Tyr phosphorylation, cellular proliferation, and Akt activation were observed with the 3E mutant. When single Glu mutants were tested, the Ser24 to Glu mutant had the greatest inhibitory effect on insulin-stimulated IRS-1 Tyr phosphorylation. PKCδ-mediated IRS-1 Ser24 phosphorylation was confirmed in cells with PKCδ catalytic domain mutants and by an RNAi method. Mechanistic studies revealed that IRS-1 with Ala and Glu point mutations at Ser24 impaired phosphatidylinositol-4,5-bisphosphate binding. In summary, our data are consistent with the hypothesis that Ser24 is a negative regulatory phosphorylation site in IRS-1

Electron streaking and dissociation in laser-assisted photoionization of molecular hydrogen

International Nuclear Information System (INIS)

Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando

2014-01-01

We report ab initio calculations on laser-assisted photoionization of the hydrogen molecule in the energy region where autoionization from doubly excited states is expected to occur. We use a UV-pump/IR-probe scheme in which an isolated attosecond UV pulse and a 750 nm IR pulse are combined. The IR pulse has a relatively low intensity (10 12 W cm −2 ), which allows us to perform a perturbative analysis of the calculated ionization probabilities differential in either electron or nuclear energy or both. We show that, for dissociative ionization, the electron energy distributions as a function of time delay exhibit unusual streaking patterns that are due to the presence of autoionizing states. These patterns significantly differ from the standard ones observed in direct single ionization of atoms and molecules. We also show that, by using such a pump–probe scheme, one can suppress autoionization from doubly excited states for time delays between 0 and 4 fs. (paper)

General active space commutator-based coupled cluster theory of general excitation rank for electronically excited states: implementation and application to ScH.

Science.gov (United States)

Hubert, Mickaël; Olsen, Jeppe; Loras, Jessica; Fleig, Timo

2013-11-21

We present a new implementation of general excitation rank coupled cluster theory for electronically excited states based on the single-reference multi-reference formalism. The method may include active-space selected and/or general higher excitations by means of the general active space concept. It may employ molecular integrals over the four-component Lévy-Leblond Hamiltonian or the relativistic spin-orbit-free four-component Hamiltonian of Dyall. In an initial application to ground- and excited states of the scandium monohydride molecule we report spectroscopic constants using basis sets of up to quadruple-zeta quality and up to full iterative triple excitations in the cluster operators. Effects due to spin-orbit interaction are evaluated using two-component multi-reference configuration interaction for assessing the accuracy of the coupled cluster results.

Photofragmentation of colloidal solutions of gold nanoparticles under femtosecond laser pulses in IR and visible ranges

International Nuclear Information System (INIS)

Danilov, P A; Zayarnyi, D A; Ionin, A A; Kudryashov, S I; Makarov, S V; Rudenko, A A; Saraeva, I N; Yurovskikh, V I; Lednev, V N; Pershin, S M

2015-01-01

The specific features of photofragmentation of sols of gold nanoparticles under focused femtosecond laser pulses in IR (1030 nm) and visible (515 nm) ranges is experimentally investigated. A high photofragmentation efficiency of nanoparticles in the waist of a pulsed laser beam in the visible range (at moderate radiation scattering) is demonstrated; this efficiency is related to the excitation of plasmon resonance in nanoparticles on the blue shoulder of its spectrum, in contrast to the regime of very weak photofragmentation in an IR-laser field of comparable intensity. Possible mechanisms of femtosecond laser photofragmentation of gold nanoparticles are discussed. (extreme light fields and their applications)

Elementary excitations and phase transformations in solids

International Nuclear Information System (INIS)

Cowley, R.A.

1985-01-01

Neutron scattering is and will continue to be a uniquely powerful tool for the study of elementary excitations and phase transformations in solids. The paper examines a few recent experiments on molecular crystals, superionic materials, paramagnetic scattering and phase transitions to see what experimental features made these experiments possible, and hence to make suggestions about future needs. It is concluded that new instruments will extend the scope of neutron scattering studies to new excitations, that there is a need for higher resolution, particularly for phase transition studies, and that it will be important to use intensity information, discrimination against unwanted inelastic processes and polarization analysis to reliably measure the excitations in new materials. (author)

Strong-Field Physics with Mid-IR Fields

Directory of Open Access Journals (Sweden)

Benjamin Wolter

2015-06-01

Full Text Available Strong-field physics is currently experiencing a shift towards the use of mid-IR driving wavelengths. This is because they permit conducting experiments unambiguously in the quasistatic regime and enable exploiting the effects related to ponderomotive scaling of electron recollisions. Initial measurements taken in the mid-IR immediately led to a deeper understanding of photoionization and allowed a discrimination among different theoretical models. Ponderomotive scaling of rescattering has enabled new avenues towards time-resolved probing of molecular structure. Essential for this paradigm shift was the convergence of two experimental tools: (1 intense mid-IR sources that can create high-energy photons and electrons while operating within the quasistatic regime and (2 detection systems that can detect the generated high-energy particles and image the entire momentum space of the interaction in full coincidence. Here, we present a unique combination of these two essential ingredients, namely, a 160-kHz mid-IR source and a reaction microscope detection system, to present an experimental methodology that provides an unprecedented three-dimensional view of strong-field interactions. The system is capable of generating and detecting electron energies that span a 6 order of magnitude dynamic range. We demonstrate the versatility of the system by investigating electron recollisions, the core process that drives strong-field phenomena, at both low (meV and high (hundreds of eV energies. The low-energy region is used to investigate recently discovered low-energy structures, while the high-energy electrons are used to probe atomic structure via laser-induced electron diffraction. Moreover, we present, for the first time, the correlated momentum distribution of electrons from nonsequential double ionization driven by mid-IR pulses.

Atomic excitation and molecular dissociation by low energy electron collisions

International Nuclear Information System (INIS)

Weyland, Marvin

2016-01-01

In this work, momentum imaging experiments have been conducted for the electron impact excitation of metastable states in noble gases and for dissociative electron attachment (DEA) in polyatomic molecules. For the electron impact excitation study a new experimental technique has been developed which is able to measure the scattering angle distribution of the electrons by detection of the momentum transfer to the atoms. Momentum transfer images have been recorded for helium and neon at fixed electron impact energy close to the excitation threshold and good agreement with current R-matrix theory calculations was found. A new momentum imaging apparatus for negative ions has been built for the purpose of studying DEA in biologically relevant molecules. During this work, DEA was investigated in the molecules ammonia, water, formic acid, furan, pyridine and in two chlorofluorocarbons. Furthermore, the change of DEA resonance energies when molecules form clusters compared to monomers was investigated in ammonia and formic acid. The experimental results of most studied molecules could be compared to recent theoretical calculations and they support further development in the theoretical description of DEA. The new apparatus built in this work also delivered a superior momentum resolution compared to existing setups. This allows the momentum imaging of heavier fragments and fragments with lower kinetic energy.

Atomic excitation and molecular dissociation by low energy electron collisions

Energy Technology Data Exchange (ETDEWEB)

Weyland, Marvin

2016-11-16

In this work, momentum imaging experiments have been conducted for the electron impact excitation of metastable states in noble gases and for dissociative electron attachment (DEA) in polyatomic molecules. For the electron impact excitation study a new experimental technique has been developed which is able to measure the scattering angle distribution of the electrons by detection of the momentum transfer to the atoms. Momentum transfer images have been recorded for helium and neon at fixed electron impact energy close to the excitation threshold and good agreement with current R-matrix theory calculations was found. A new momentum imaging apparatus for negative ions has been built for the purpose of studying DEA in biologically relevant molecules. During this work, DEA was investigated in the molecules ammonia, water, formic acid, furan, pyridine and in two chlorofluorocarbons. Furthermore, the change of DEA resonance energies when molecules form clusters compared to monomers was investigated in ammonia and formic acid. The experimental results of most studied molecules could be compared to recent theoretical calculations and they support further development in the theoretical description of DEA. The new apparatus built in this work also delivered a superior momentum resolution compared to existing setups. This allows the momentum imaging of heavier fragments and fragments with lower kinetic energy.

Brome isotope selective control of CF3Br molecule clustering by IR laser radiation in gas-dynamic expansion of CF3Br - Ar mixture

Science.gov (United States)

Apatin, V. M.; Lokhman, V. N.; Makarov, G. N.; Ogurok, N.-D. D.; Ryabov, E. A.

2018-02-01

We report the results of research on the experimental control of CF3Br molecule clustering under gas-dynamic expansion of the CF3Br - Ar mixture at a nozzle exit by using IR laser radiation. A cw CO2 laser is used for exciting molecules and clusters in the beam and a time-of-flight mass-spectrometer with laser UV ionisation of particles for their detection. The parameters of the gas above the nozzle are determined (compositions and pressure) at which intensive molecule clustering occurs. It is found that in the case of the CF3Br gas without carrier when the pressure P0 above the nozzle does not exceed 4 atm, molecular clusters actually are not generated in the beam. If the gas mixture of CF3Br with argon is used at a pressure ratio 1 : N, where N >= 3, and the total pressure above the nozzle is P0 >= 2 atm, then there occurs molecule clustering. We study the dependences of the efficiency of suppressing the molecule clustering on parameters of the exciting pulse, gas parameters above the nozzle, and on a distance of the molecule irradiation zone from the nozzle exit section. It is shown that in the case of resonant vibrational excitation of gas-dynamically cooled CF3Br molecules at the nozzle exit one can realise isotope-selective suppression of molecule clustering with respect to bromine isotopes. With the CF3Br - Ar mixtures having the pressure ratio 1 : 3 and 1 : 15, the enrichment factors obtained with respect to bromine isotopes are kenr ≈ 1.05 ± 0.005 and kenr ≈ 1.06 ± 0.007, respectively, under jet irradiation by laser emission in the 9R(30) line (1084.635 cm-1). The results obtained let us assume that this method can be used to control clustering of molecules comprising heavy element isotopes, which have a small isotopic shift in IR absorption spectra.

Multicomponent Time-Dependent Density Functional Theory: Proton and Electron Excitation Energies.

Science.gov (United States)

Yang, Yang; Culpitt, Tanner; Hammes-Schiffer, Sharon

2018-04-05

The quantum mechanical treatment of both electrons and protons in the calculation of excited state properties is critical for describing nonadiabatic processes such as photoinduced proton-coupled electron transfer. Multicomponent density functional theory enables the consistent quantum mechanical treatment of more than one type of particle and has been implemented previously for studying ground state molecular properties within the nuclear-electronic orbital (NEO) framework, where all electrons and specified protons are treated quantum mechanically. To enable the study of excited state molecular properties, herein the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. Initial applications to FHF - and HCN illustrate that NEO-TDDFT provides accurate proton and electron excitation energies within a single calculation. As its computational cost is similar to that of conventional electronic TDDFT, the NEO-TDDFT approach is promising for diverse applications, particularly nonadiabatic proton transfer reactions, which may exhibit mixed electron-proton vibronic excitations.

Cell surface GRP78 facilitates hepatoma cells proliferation and migration by activating IGF-IR.

Science.gov (United States)

Yin, Yancun; Chen, Chen; Chen, Jinliang; Zhan, Renhui; Zhang, Qiang; Xu, Xiaoyan; Li, Defang; Li, Minjing

2017-07-01

The 78kDa glucose regulated protein (GRP78) is a multifunctional chaperone that is involved in a variety of cellular processes. Insulin like growth factor I receptor (IGF-IR) often aberrant expresses in many types of tumor cells. The IGF-IR signaling plays key roles in carcinogenesis and maintenance of the malignant phenotype. The crosstalk between GRP78 and IGF-IR molecules has not well been illuminated. Here, we demonstrated a reciprocal regulation of GRP78 expression and IGF-IR pathway activation. IGF-I induced GRP78 expression in hepatoma cells. IGF-IR knockdown or IGF-IR inhibitor repressed GRP78 expression. Both phosphatidylinositol 3-kianase (PI3K) and mitogen-activated protein kinase (MAPK) pathways involved in IGF-I induction of GRP78 expression. Interestingly, treatment of hepatoma cells with IGF-I re-distributes GRP78 from endoplasmic reticulum (ER) to cell surface and promotes its physical interaction with IGF-IR. Also, GRP78 promotes IGF-IR phosphorylation and activation. Blocked of GRP78 by small interfering RNA or inhibition of GRP78 function by (-)-epigallocatechin gallate (EGCG) blocks IGF-I induced IGF-IR phosphorylation and its downstream signaling. Further, blocked cell surface GRP78 with antibody inhibits IGF-I stimulated cellular proliferation and migration. These data reveal an essential role for the molecular chaperone GRP78 in IGF-IR signaling and implicate the use of GRP78 inhibitors in blocking IGF-IR signaling in hepatoma cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Conformality or confinement: (IR)relevance of topological excitations

Energy Technology Data Exchange (ETDEWEB)

Poppitz, Erich; /Toronto U.; Unsal, Mithat; /SLAC /Stanford U., Phys. Dept.

2010-08-26

What distinguishes two asymptotically-free non-abelian gauge theories on R{sup 4}, one of which is just below the conformal window boundary and confines, while the other is slightly above the boundary and flows to an infrared conformal field theory? In this work, we aim to answer this question for non-supersymmetric Yang-Mills theories with fermions in arbitrary chiral or vectorlike representations. We use the presence or absence of mass gap for gauge fluctuations as an identifier of the infrared behavior. With the present-day understanding of such gauge theories, the mass gap for gauge fluctuations cannot be computed on R{sup 4}. However, recent progress allows its non-perturbative computation on R{sup 3} x S{sup 1} by using either the twisted partition function or deformation theory, for a range of sizes of S{sup 1} depending on the theory. For small number of fermions, N{sub f}, we show that the mass gap increases with increasing radius, due to the non-dilution of monopoles and bions - the topological excitations relevant for confinement on R{sup 3} x S{sup 1}. For sufficiently large N{sub f}, we show that the mass gap decreases with increasing radius. In a class of theories, we claim that the decompactification limit can be taken while remaining within the region of validity of semiclassical techniques, giving the first examples of semiclassically solvable Yang-Mills theories at any size S{sup 1}. For general non-supersymmetric vectorlike or chiral theories, we conjecture that the change in the behavior of the mass gap on R{sup 3} x S{sup 1} as a function of the radius occurs near the lower boundary of the conformal window and give non-perturbative estimates of its value. For vectorlike theories, we compare our estimates of the conformal window with existing lattice results, truncations of the Schwinger-Dyson equations, NSVZ beta function-inspired estimates, and degree of freedom counting criteria. For multi-generation chiral gauge theories, to the best of our

Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles

Science.gov (United States)

Gupta, Gajendra; Murray, Benjamin S.; Dyson, Paul J.; Therrien, Bruno

2013-01-01

The neutral dinuclear complexes [(η5-C5Me5)2Rh2(μ-dhnq)Cl2] (1) and [(η5-C5Me5)2Ir2(μ-dhnq)Cl2] (2) (dhnqH2 = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η5-C5Me5)M(μ-Cl)Cl]2 (M = Rh, Ir) with dhnqH2 in the presence of CH3COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF3SO3, affords the corresponding tetranuclear metalla-rectangles [(η5-C5Me5)4M4(μ-dhnq)2(μ-L)2]4+ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4′-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh, 7; M = Ir, 8). All complexes were isolated as their triflate salts and were fully characterized by infrared, 1H and 13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles 3–8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC50 values in the low micromolar range. PMID:28788394

Synthesis, Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III and Ir(III Tetranuclear Metalla-Cycles

Directory of Open Access Journals (Sweden)

Gajendra Gupta

2013-11-01

Full Text Available The neutral dinuclear complexes [(η5-C5Me52Rh2(μ-dhnqCl2] (1 and [(η5-C5Me52Ir2(μ-dhnqCl2] (2 (dhnqH2 = 5,8-dihydroxy-1,4-naphthoquinone were obtained from the reaction of [(η5-C5Me5M(μ-ClCl]2 (M = Rh, Ir with dhnqH2 in the presence of CH3COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridylethylene, in the presence of AgCF3SO3, affords the corresponding tetranuclear metalla-rectangles [(η5-C5Me54M4(μ-dhnq2(μ-L2]4+ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4′-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridylethylene, M = Rh, 7; M = Ir, 8. All complexes were isolated as their triflate salts and were fully characterized by infrared, 1H and 13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles 3–8 was evaluated against the human ovarian A2780 (cisplatin sensitive and A2780cisR (cisplatin resistant cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC50 values in the low micromolar range.

Down-regulation of honey bee IRS gene biases behavior toward food rich in protein.

Directory of Open Access Journals (Sweden)

Ying Wang

2010-04-01

Full Text Available Food choice and eating behavior affect health and longevity. Large-scale research efforts aim to understand the molecular and social/behavioral mechanisms of energy homeostasis, body weight, and food intake. Honey bees (Apis mellifera could provide a model for these studies since individuals vary in food-related behavior and social factors can be controlled. Here, we examine a potential role of peripheral insulin receptor substrate (IRS expression in honey bee foraging behavior. IRS is central to cellular nutrient sensing through transduction of insulin/insulin-like signals (IIS. By reducing peripheral IRS gene expression and IRS protein amount with the use of RNA interference (RNAi, we demonstrate that IRS influences foraging choice in two standard strains selected for different food-hoarding behavior. Compared with controls, IRS knockdowns bias their foraging effort toward protein (pollen rather than toward carbohydrate (nectar sources. Through control experiments, we establish that IRS does not influence the bees' sucrose sensory response, a modality that is generally associated with food-related behavior and specifically correlated with the foraging preference of honey bees. These results reveal a new affector pathway of honey bee social foraging, and suggest that IRS expressed in peripheral tissue can modulate an insect's foraging choice between protein and carbohydrate sources.

Quantum computational studies, spectroscopic (FT-IR, FT-Raman and UV-Vis) profiling, natural hybrid orbital and molecular docking analysis on 2,4 Dibromoaniline

Science.gov (United States)

Abraham, Christina Susan; Prasana, Johanan Christian; Muthu, S.; Rizwana B, Fathima; Raja, M.

2018-05-01

The research exploration will comprise of investigating the molecular structure, vibrational assignments, bonding and anti-bonding nature, nonlinear optical, electronic and thermodynamic nature of the molecule. The research is conducted at two levels: First level employs the spectroscopic techniques - FT-IR, FT-Raman and UV-Vis characterizing techniques; at second level the data attained experimentally is analyzed through theoretical methods using and Density Function Theories which involves the basic principle of solving the Schrodinger equation for many body systems. A comparison is drawn between the two levels and discussed. The probability of the title molecule being bio-active theoretically proved by the electrophilicity index leads to further property analyzes of the molecule. The target molecule is found to fit well with Centromere associated protein inhibitor using molecular docking techniques. Higher basis set 6-311++G(d,p) is used to attain results more concurrent to the experimental data. The results of the organic amine 2, 4 Dibromoaniline is analyzed and discussed.

Excitation transfer pathways in excitonic aggregates revealed by the stochastic Schrödinger equation

Energy Technology Data Exchange (ETDEWEB)

Abramavicius, Vytautas, E-mail: vytautas.ab@gmail.com; Abramavicius, Darius, E-mail: darius.abramavicius@ff.vu.lt [Faculty of Physics, Department of Theoretical Physics, Vilnius University, Saulėtekio 9, LT-10222 Vilnius (Lithuania)

2014-02-14

We derive the stochastic Schrödinger equation for the system wave vector and use it to describe the excitation energy transfer dynamics in molecular aggregates. We suggest a quantum-measurement based method of estimating the excitation transfer time. Adequacy of the proposed approach is demonstrated by performing calculations on a model system. The theory is then applied to study the excitation transfer dynamics in a photosynthetic pigment-protein Fenna-Matthews-Olson (FMO) aggregate using both the Debye spectral density and the spectral density obtained from earlier molecular dynamics simulations containing strong vibrational high-frequency modes. The obtained results show that the excitation transfer times in the FMO system are affected by the presence of the vibrational modes; however, the transfer pathways remain the same.

Direct Electron Impact Excitation of Rydberg-Valence States of Molecular Nitrogen

Science.gov (United States)

Malone, C. P.; Johnson, P. V.; Liu, X.; Ajdari, B.; Muleady, S.; Kanik, I.; Khakoo, M. A.

2012-12-01

Collisions between electrons and neutral N2 molecules result in emissions that provide an important diagnostic probe for understanding the ionospheric energy balance and the effects of space weather in upper atmospheres. Also, transitions to singlet ungerade states cause N2 to be a strong absorber of solar radiation in the EUV spectral range where many ro-vibrational levels of these Rydberg-valence (RV) states are predissociative. Thus, their respective excitation and emission cross sections are important parameters for understanding the [N]/[N2] ratio in the thermosphere of nitrogen dominated atmospheres. The following work provides improved constraints on absolute and relative excitation cross sections of numerous RV states of N2, enabling more physically accurate atmospheric modeling. Here, we present recent integral cross sections (ICSs) for electron impact excitation of RV states of N2 [6], which were based on the differential cross sections (DCSs) derived from electron energy-loss (EEL) spectra of [5]. This work resulted in electronic excitation cross sections over the following measured vibrational levels: b 1Πu (v‧=0-14), c3 1Πu (v‧=0-3), o3 1Πu (v‧=0-3), b‧ 1Σu+ (v‧=0-10), c‧4 1Σu+ (v‧=0-3), G 3Πu (v‧=0-3), and F 3Πu (v‧=0-3). We further adjusted the cross sections of the RV states by extending the vibronic contributions to unmeasured v‧-levels via the relative excitation probabilities (REPs) as discussed in [6]. This resulted in REP-scaled ICSs over the following vibrational levels for the singlet ungerade states: b(0-19), c3(0-4), o3(0-4), b‧(0-16), and c‧4(0-8). Comparison of the ICSs of [6] with available EEL based measurements, theoretical calculations, and emission based work generally shows good agreement within error estimations, except with the recent reevaluation provided by [1]. Further, we have extended these results, using the recent EEL data of [3], to include the unfolding of better resolved features above ~13

Atomic and molecular excitation mechanisms in the interstellar medium

International Nuclear Information System (INIS)

Sternberg, A.

1986-01-01

The detailed infrared response of dense molecular hydrogen gas to intense ultraviolet radiation fields in photodissociation regions is presented. The thermal and chemical structures of photodissociation regions are analyzed, and the relationship between the emission by molecular hydrogen and trace atomic and molecular species is explored. The ultraviolet spectrum of radiation generated by cosmic rays inside dense molecular clouds is presented, and the resulting rates of photodissociation for a variety of interstellar molecules are calculated. Effects of this radiation on the chemistry of dense molecular clouds are discussed, and it is argued that the cosmic ray induced photons will significantly inhibit the production of complex molecular species. It is argued that the annihilation of electrons and positrons at the galactic center may result in observable infrared line emission by atomic hydrogen. A correlation between the intensity variations of the 511 keV line and the hydrogen infrared lines emitted by the annihilation region is predicted. The observed infrared fluxes from compact infrared sources at the galactic center may be used to constrain theories of pair production there

Cluster-derived Ir-Sn/SiO2 catalysts for the catalytic dehydrogenation of propane: A spectroscopic study

KAUST Repository

Gallo, Alessandro

2013-01-01

Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir 4(CO)10(SnCl3)2] and NEt 4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9) 4 onto pre-formed Ir metal particles. These solids possess promising properties, in terms of selectivity, as catalysts for propane dehydrogenation to propene. Detailed CO-adsorption DRIFTS, XANES and EXAFS characterization studies have been performed on these systems in order to compare the structural and electronic evolution of systems in relation to the nature of the Ir-Sn bonds present in the precursor compounds and to propose a structural model of the Ir-Sn species present at the silica surface of the final catalyst. © 2013 The Royal Society of Chemistry.

Molecular gas properties of a lensed star-forming galaxy at z 3.6: a case study

Science.gov (United States)

Dessauges-Zavadsky, M.; Zamojski, M.; Rujopakarn, W.; Richard, J.; Sklias, P.; Schaerer, D.; Combes, F.; Ebeling, H.; Rawle, T. D.; Egami, E.; Boone, F.; Clément, B.; Kneib, J.-P.; Nyland, K.; Walth, G.

2017-09-01

We report on the galaxy MACSJ0032-arc at zCO = 3.6314 discovered during the Herschel Lensing snapshot Survey of massive galaxy clusters, and strongly lensed by the cluster MACS J0032.1+1808. The successful detections of its rest-frame ultraviolet (UV), optical, far-infrared (FIR), millimeter, and radio continua, and of its CO emission enable us to characterize, for the first time at such a high redshift, the stellar, dust, and molecular gas properties of a compact star-forming galaxy with a size smaller than 2.5 kpc, a fairly low stellar mass of 4.8+ 0.5-1.0 × 109M⊙, and a moderate IR luminosity of 4.8+ 1.2-0.6 × 1011L⊙. By combining the stretching effect of the lens with the high angular resolution imaging of the CO(1-0) line emission and the radio continuum at 5 GHz, we find that the bulk of the molecular gas mass and star formation seems to be spatially decoupled from the rest-frame UV emission. About 90% of the total star formation rate is undetected at rest-frame UV wavelengths because of severe obscuration by dust, but is seen through the thermal FIR dust emission and the radio synchrotron radiation. The observed CO(4-3) and CO(6-5) lines demonstrate that high-J transitions, at least up to J = 6, remain excited in this galaxy, whose CO spectral line energy distribution resembles that of high-redshift submm galaxies, even though the IR luminosity of MACSJ0032-arc is ten times lower. This high CO excitation is possibly due to the compactness of the galaxy. We find evidence that this high CO excitation has to be considered in the balance when estimating the CO-to-H2 conversion factor. Indeed, the respective CO-to-H2 conversion factors as derived from the correlation with metallicity and the FIR dust continuum can only be reconciled if excitation is accounted for. The inferred depletion time of the molecular gas in MACSJ0032-arc supports the decrease in the gas depletion timescale of galaxies with redshift, although to a lesser degree than predicted by

THE ORION FINGERS: NEAR-IR SPECTRAL IMAGING OF AN EXPLOSIVE OUTFLOW

Energy Technology Data Exchange (ETDEWEB)

Youngblood, Allison; Bally, John [Department of Astrophysical and Planetary Sciences, University of Colorado, UCB 389, Boulder, CO 80309 (United States); Ginsburg, Adam, E-mail: allison.youngblood@colorado.edu [ESO Headquarters, Karl-Schwarzschild-Strasse 2, D-85748 Garching bei München (Germany)

2016-06-01

We present near-IR (1.1–2.4 μ m) position–position–velocity cubes of the 500 year old Orion BN/KL explosive outflow with spatial resolution 1″ and spectral resolution 86 km s{sup −1}. We construct integrated intensity maps free of continuum sources of 15 H{sub 2} and [Fe ii] lines while preserving kinematic information of individual outflow features. Included in the detected H{sub 2} lines are the 1-0 S(1) and 1-0 Q(3) transitions, allowing extinction measurements across the outflow. Additionally, we present dereddened flux ratios for over two dozen outflow features to allow for the characterization of the true excitation conditions of the BN/KL outflow. All of the ratios show the dominance of the shock excitation of the H{sub 2} emission, although some features exhibit signs of fluorescent excitation from stellar radiation or J-type shocks. We also detect tracers of the PDR/ionization front north of the Trapezium stars in [O i] and [Fe ii] and analyze other observed outflows not associated with the BN/KL outflow.

A coherent modified Redfield theory for excitation energy transfer in molecular aggregates

Energy Technology Data Exchange (ETDEWEB)

Hwang-Fu, Yu-Hsien; Chen, Wei; Cheng, Yuan-Chung, E-mail: yuanchung@ntu.edu.tw

2015-02-02

Highlights: • A CMRT method for coherent energy transfer in molecular aggregates was developed. • Applicability of the method was verified in two-site systems with various parameters. • CMRT accurately describes population dynamics in the FMO-complex. • The method is accurate in a large parameter space and computationally efficient. - Abstract: Excitation energy transfer (EET) is crucial in photosynthetic light harvesting, and quantum coherence has been recently proven to be a ubiquitous phenomenon in photosynthetic EET. In this work, we derive a coherent modified Redfield theory (CMRT) that generalizes the modified Redfield theory to treat coherence dynamics. We apply the CMRT method to simulate the EET in a dimer system and compare the results with those obtained from numerically exact path integral calculations. The comparison shows that CMRT provides excellent computational efficiency and accuracy within a large EET parameter space. Furthermore, we simulate the EET dynamics in the FMO complex at 77 K using CMRT. The results show pronounced non-Markovian effects and long-lasting coherences in the ultrafast EET, in excellent agreement with calculations using the hierarchy equation of motion approach. In summary, we have successfully developed a simple yet powerful framework for coherent EET dynamics in photosynthetic systems and organic materials.

Matrix isolation FT-IR spectroscopy and molecular orbital study of sarcosine methyl ester

Science.gov (United States)

Gómez-Zavaglia, A.; Fausto, R.

2004-02-01

N-methylglycine methyl ester (sarcosine-Me) has been studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) and 6-31++G(d,p) basis set, respectively. Twelve different conformers were located in the potential energy surface of the studied compound, with the ASC conformer being the ground conformational state. This form is analogous to the dimethylglycine methyl ester most stable conformer and is characterized by a NH⋯O intramolecular hydrogen bond; in this form, the ester group assumes the cis configuration and the OC-C-N and Lp-N-C-C (where Lp is the nitrogen lone electron pair) dihedral angles are ca. -17.8 and 171.3°, respectively. The second most stable conformer ( GSC) differs from the ASC conformer essentially in the conformation assumed by the methylamino group, which in this case is gauche ( Lp-N-C-C dihedral angle equal to 79.4°). On the other hand, the third most stable conformer ( AAC) differs from the most stable form in the conformation of the OC-C-N axis (151.4°). These three forms were predicted to differ in energy by less than ca. 5 kJ mol -1 and represent ≈95% of the total conformational population at room temperature. FT-IR spectra were obtained for sarcosine-Me isolated in argon matrices (T=9 K) revealing the presence in the matrices of the three lowest energy conformers predicted by the calculations. The matrices were prepared by deposition of the vapour of the compound using two different nozzle temperatures, 25 and 60 °C. The relative populations of the three conformers trapped in the matrices were found to be consistent with occurrence of conformational cooling during matrix deposition and with a stabilization of the most polar GSC and AAC conformers in the matrices compared to the gas phase. Indeed, like it was previously observed for the methyl ester of dimethylglycine [Phys. Chem. Chem. Phys. 5 (2003) 52] the different

Spectroscopic [FT-IR and FT-Raman] and theoretical [UV-Visible and NMR] analysis on α-Methylstyrene by DFT calculations

Science.gov (United States)

Karthikeyan, N.; Joseph Prince, J.; Ramalingam, S.; Periandy, S.

2015-05-01

In the present research work, the FT-IR, FT-Raman and 13C and 1H NMR spectra of the α-Methylstyrene were recorded. The observed fundamental frequencies in finger print as well as functional group regions were assigned according to their uniqueness region. The Gaussian computational calculations are carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The impact of the presence of vinyl group in phenyl structure of the compound is investigated. The modified vibrational pattern of the molecule associated vinyl group was analyzed. Moreover, 13C NMR and 1H NMR were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed.

General review of multispectral cooled IR development at CEA-Leti, France

Science.gov (United States)

Boulard, F.; Marmonier, F.; Grangier, C.; Adelmini, L.; Gravrand, O.; Ballet, P.; Baudry, X.; Baylet, J.; Badano, G.; Espiau de Lamaestre, R.; Bisotto, S.

2017-02-01

Multicolor detection capabilities, which bring information on the thermal and chemical composition of the scene, are desirable for advanced infrared (IR) imaging systems. This communication reviews intra and multiband solutions developed at CEA-Leti, from dual-band molecular beam epitaxy grown Mercury Cadmium Telluride (MCT) photodiodes to plasmon-enhanced multicolor IR detectors and backside pixelated filters. Spectral responses, quantum efficiency and detector noise performances, pros and cons regarding global system are discussed in regards to technology maturity, pixel pitch reduction, and affordability. From MWIR-LWIR large band to intra MWIR or LWIR bands peaked detection, results underline the full possibility developed at CEA-Leti.

Pressure-induced transformations of molecular boron hydride

CERN Document Server

Nakano, S; Gregoryanz, E A; Goncharov, A F; Mao Ho Kwang

2002-01-01

Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV.

Pressure-induced transformations of molecular boron hydride

International Nuclear Information System (INIS)

Nakano, Satoshi; Hemley, Russell J; Gregoryanz, Eugene A; Goncharov, Alexander F; Mao, Ho-kwang

2002-01-01

Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV

Reprocessing WFC3/IR Exposures Affected by Time-Variable Backgrounds

Science.gov (United States)

Brammer, G.

2016-11-01

The background seen in WFC3/IR observations frequently shows strong time-dependent behavior above the constant flux expected for zodiacal continuum light. This is often caused by an emission line of helium at 1.083 μm excited in the sun-illuminated upper atmosphere, when seen in the filters (F105W, F110W) and grisms (G102, G141) sensitive to the feature. The default behavior of the calwf3 pipeline assumes constant source-plus-background fluxes when it performs up-the-ramp fitting to identify cosmic rays and determine the average count rate within a MULTIACCUM IR exposure. calwf3 provides undesirable results in the presence of strongly variable backgrounds, primarily in the form of elevated and non-Gaussian noise in the FLT products. Here we describe methods to improve the noise properties of the reduced products. In the first, we simply turn off the calwf3 crcorr step, treating the IR detector as if it were a CCD, i.e., accumulating flux and reading it out at the end of the exposure. Next, we artificially flatten the ramps in the IMA products and then allow calwf3 to proceed as normal fitting the ramp and identifying CRs. Either of these procedures enable recovery of datasets otherwise corrupted beyond repair and have no discernible effects on photometry of sources in deep combined images.

Structure and linear spectroscopic properties of near IR polymethine dyes

International Nuclear Information System (INIS)

Webster, Scott; Padilha, Lazaro A.; Hu Honghua; Przhonska, Olga V.; Hagan, David J.; Van Stryland, Eric W.; Bondar, Mikhail V.; Davydenko, Iryna G.; Slominsky, Yuriy L.; Kachkovski, Alexei D.

2008-01-01

We performed a detailed experimental investigation and quantum-chemical analysis of a new series of near IR polymethine dyes with 5-butyl-7,8-dihydrobenzo[cd]furo[2,3-f]indolium terminal groups. We also synthesized and studied two neutral dyes, squaraine and tetraone, with the same terminal groups and performed a comparison of the spectroscopic properties of this set of 'near IR' dyes (polymethine, squaraine, and tetraone) with an analogous set of 'visible' dyes with simpler benzo[e]indolium terminal groups. From these measurements, we find that the dyes with dihydrobenzo[cd]furo[2,3-f]indolium terminal groups are characterized by a remarkably large shift ∼300 nm (∼200 nm for tetraone) of their absorption bands towards the red region. We discuss the difference in electronic structure for these molecules and show that the 'near IR' dyes are characterized by an additional weak fluorescence band from the higher lying excited states connected with the terminal groups. Absorption spectra for the longest polymethines are solvent-dependent and are characterized by a broadening of the main band in polar solvents, which is explained by ground state symmetry breaking and reduced charge delocalization within the polymethine chromophore. The results of these experiments combined with the agreement of quantum chemical calculations moves us closer to a predictive capability for structure-property relations in cyanine-like molecules

Molecular oxygen adsorption and dissociation on Au12M clusters with M = Cu, Ag or Ir

Science.gov (United States)

Jiménez-Díaz, Laura M.; Pérez, Luis A.

2018-03-01

In this work, we present a density functional theory study of the structural and electronic properties of isolated neutral clusters of the type Au12M, with M = Cu, Ag, or Ir. On the other hand, there is experimental evidence that gold-silver, gold-copper and gold-iridium nanoparticles have an enhanced catalytic activity for the CO oxidation reaction. In order to address these phenomena, we also performed density functional calculations of the adsorption and dissociation of O2 on these nanoparticles. Moreover, to understand the effects of Cu, Ag, and Ir impurity atoms on the dissociation of O2, we also analyze this reaction in the corresponding pure gold cluster. The results indicate that the substitution of one gold atom in a Au13 cluster by Ag, Cu or Ir diminishes the activation energy barrier for the O2 dissociation by nearly 1 eV. This energy barrier is similar for Au12Ag and Au12Cu, whereas for Au12Ir is even lower. These results suggest that the addition of other transition metal atoms to gold nanoclusters can enhance their catalytic activity towards the CO oxidation reaction, independently of the effect that the substrate could have on supported nanoclusters.

HIFISTARS Herschel/HIFI observations of VY Canis Majoris. Molecular-line inventory of the envelope around the largest known star

Science.gov (United States)

Alcolea, J.; Bujarrabal, V.; Planesas, P.; Teyssier, D.; Cernicharo, J.; De Beck, E.; Decin, L.; Dominik, C.; Justtanont, K.; de Koter, A.; Marston, A. P.; Melnick, G.; Menten, K. M.; Neufeld, D. A.; Olofsson, H.; Schmidt, M.; Schöier, F. L.; Szczerba, R.; Waters, L. B. F. M.

2013-11-01

Aims: The study of the molecular gas in the circumstellar envelopes of evolved stars is normally undertaken by observing lines of CO (and other species) in the millimetre-wave domain. In general, the excitation requirements of the observed lines are low at these wavelengths, and therefore these observations predominantly probe the cold outer envelope while studying the warm inner regions of the envelopes normally requires sub-millimetre (sub-mm) and far-infrared (FIR) observational data. Methods: To gain insight into the physical conditions and kinematics of the warm (100-1000 K) gas around the red hyper-giant VY CMa, we performed sensitive high spectral resolution observations of molecular lines in the sub-mm/FIR using the HIFI instrument of the Herschel Space Observatory. We observed CO, H2O, and other molecular species, sampling excitation energies from a few tens to a few thousand K. These observations are part of the Herschel guaranteed time key program HIFISTARS. Results: We detected the J = 6-5, J = 10-9, and J = 16-15 lines of 12CO and 13CO at ~100, 300, and 750 K above the ground state (and the 13CO J = 9-8 line). These lines are crucial for improving the modelling of the internal layers of the envelope around VY CMa. We also detected 27 lines of H2O and its isotopomers, and 96 lines of species such as NH3, SiO, SO, SO2 HCN, OH and others, some of them originating from vibrationally excited levels. Three lines were not unambiguously assigned. Conclusions: Our observations confirm that VY CMa's envelope must consist of two or more detached components. The molecular excitation in the outer layers is significantly lower than in the inner ones, resulting in strong self-absorbed profiles in molecular lines that are optically thick in this outer envelope, for instance, low-lying lines of H2O. Except for the most abundant species, CO and H2O, most of the molecular emission detected at these sub-mm/FIR wavelengths arise from the central parts of the envelope. The

Nonlinear optical response of chalcogenide glassy semiconductors in the IR and THz ranges studied with the femtosecond resolution in time

DEFF Research Database (Denmark)

Romanova, E.; Guizard, S.; Wang, Tianwu

2017-01-01

Two time-resolved experimental methods have been used for characterization of the non-linear optical response of chalcogenide glasses of the system As-S-Se-Te in IR and THz ranges upon excitation by femtosecond laser pulses at 800 nm wavelength. Photoinduced conductivity and refractivity were stu...

Facile Dehydrogenation of Ethane on the IrO2(110) Surface.

Science.gov (United States)

Bian, Yingxue; Kim, Minkyu; Li, Tao; Asthagiri, Aravind; Weaver, Jason F

2018-02-21

Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO 2 (110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO 2 (110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to CO x species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO 2 (110) during TPRS. Partial hydrogenation of the IrO 2 (110) surface is found to enhance ethylene production from ethane while suppressing oxidation to CO x species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO 2 (110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO 2 (110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.

Investigation of hybrid molecular material prepared by ionic liquid ...

Indian Academy of Sciences (India)

Wintec

Near IR spectral region (1000–2500 nm) shows the elimination of water in the compound which ... 1-Butyl 3-methyl imidazolium bromide; molecular material; phosphotungstic acid; near IR. ..... attributable to the first overtone of hydroxyl groups,.

Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

International Nuclear Information System (INIS)

Ye, ChuanXiang; Zhao, Yi; Liang, WanZhen

2015-01-01

The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT

Study of highly excited high spin states via the (HI, α) reaction

International Nuclear Information System (INIS)

Kubono, S.

1982-01-01

Three subjects are discussed in this paper. 1) The mechanism of (HI, α) reactions is briefly studied. 2) Possible excitation of molecular resonance states of 12 C- 12 C in 24 Mg through the 12 C( 16 O, α) 24 Mg reaction were investigated. A precise measurement of the level widths in 24 Mg did not support the previous report that the molecular states seen in 12 C + 12 C scattering had been excited in the transfer reaction 12 C( 16 O, α) 24 Mg. 3) Highly excited states in 28 Si, which have a large parentage of 12 C- 16 O, were also studied via the 12 C( 20 Ne, α) 28 Si reaction. An angular correlation measurement revealed the lowest 8 + and 10 + states at 14.00 and 15.97 MeV, respectively, which were selectively excited in the 12 C( 20 Ne, α) reaction. These results suggest a possible new band in 28 Si. (author)

Mechanical feedback in the molecular ISM of luminous IR galaxies

NARCIS (Netherlands)

Loenen, A. F.; Spaans, M.; Baan, W. A.; Meijerink, R.

Aims. Molecular emission lines originating in the nuclei of luminous infra-red galaxies are used to determine the physical properties of the nuclear ISM in these systems. Methods. A large observational database of molecular emission lines is compared with model predictions that include heating by UV

Excitation of Molecular Hydrogen in the Orion Bar Photodissociation Region from a Deep Near-infrared IGRINS Spectrum

Science.gov (United States)

Kaplan, Kyle F.; Dinerstein, Harriet L.; Oh, Heeyoung; Mace, Gregory N.; Kim, Hwihyun; Sokal, Kimberly R.; Pavel, Michael D.; Lee, Sungho; Pak, Soojong; Park, Chan; Sok Oh, Jae; Jaffe, Daniel T.

2017-04-01

We present a deep near-infrared spectrum of the Orion Bar Photodissociation Region (PDR) taken with the Immersion Grating INfrared Spectrometer (IGRINS) on the 2.7 m telescope at the McDonald Observatory. IGRINS has high spectral resolution (R˜ {{45,000}}) and instantaneous broad wavelength coverage (1.45-2.45 μm), enabling us to detect 87 emission lines from rovibrationally excited molecular hydrogen (H2) that arise from transitions out of 69 upper rovibration levels of the electronic ground state. These levels cover a large range of rotational and vibrational quantum numbers and excitation energies, making them excellent probes of the excitation mechanisms of H2 and physical conditions within the PDR. The Orion Bar PDR is thought to consist of cooler high density clumps or filaments (T=50{--}250 K, {n}H={10}5{--}{10}7 cm-3) embedded in a warmer lower density medium (T=250{--}1000 K, {n}H={10}4{--}{10}5 cm-3). We fit a grid of constant temperature and density Cloudy models, which recreate the observed H2 level populations well, to constrain the temperature to a range of 600-650 K and the density to {n}H=2.5× {10}3{--}{10}4 cm-3. The best-fit model gives T = 625 K and {n}H=5× {10}3 cm-3. This well-constrained warm temperature is consistent with kinetic temperatures found by other studies for the Orion Bar’s lower density medium. However, the range of densities well fit by the model grid is marginally lower than those reported by other studies. We could be observing lower density gas than the surrounding medium, or perhaps a density-sensitive parameter in our models is not properly estimated.

Low temperature FT-IR and molecular orbital study of N,N-dimethylglycine methyl ester: Proof for different ground conformational states in gas phase and in condensed media

OpenAIRE

Gómez-Zavaglia, A.; Fausto, R.

2002-01-01

N,N-dimethylglycine methyl ester (DMG-Me) was studied by FT-IR spectroscopy under several experimental conditions, including low temperature solid state and isolated in low temperature inert gas matrices, and by molecular orbital calculations. In agreement with the theoretical predictions, the experimental data show that in the gaseous phase the most stable conformer (ASC) has the ester group in cis configuration and the N–C–CO and Lp–N–C–C (Lp=lone electron pair) dihedral angles equal to 0° ...

Reaction dynamics of electronically excited alkali atoms with simpler molecules

International Nuclear Information System (INIS)

Weiss, P.S.; Mestdagh, J.M.; Schmidt, H.; Vernon, M.F.; Covinsky, M.H.; Balko, B.A.; Lee, Y.T.

1985-05-01

The reactions of electronically excited sodium atoms with simple molecules have been studied in crossed molecular beams experiments. Electronically excited Na(3 2 P/sub 3/2/, 4 2 D/sub 5/2/, and 5 2 S/sub 1/2/) were produced by optical pumping using single frequency dye lasers. The effects of the symmetry, and the orientation and alignment of the excited orbital on the chemical reactivity, and detailed information on the reaction dynamics were derived from measurements of the product angular and velocity distributions. 12 refs., 9 figs

Molecular hydrogen emission from cold condensations in NGC 2440

International Nuclear Information System (INIS)

Reay, N.K.; Walton, N.A.

1988-01-01

Observations are reported of the ν = 1-0 S(1) line of molecular hydrogen in the high-excitation planetary nebula NGC 2440. The emission is particularly strong at the positions of the two bright condensations which lie well within the H II region and close to the position of the very hot T ≅ 350 000 K central star. The emission is consistent with an excited molecular hydrogen mass of ≅ 2-4 x 10 -5 solar mass in the condensations, and the total mass of excited molecular hydrogen associated with the H II region is estimated to be ≅ 6.1 x 10 -3 solar mass. We show that radiation pressure from the central star is insufficient to excite the S(1) line emission. (author)

Deciphering excited state evolution in halorhodopsin with stimulated emission pumping.

Science.gov (United States)

Bismuth, Oshrat; Komm, Pavel; Friedman, Noga; Eliash, Tamar; Sheves, Mordechai; Ruhman, Sanford

2010-03-04

The primary photochemical dynamics of Hb. pharaonis Halorhodopsin (pHR) are investigated by femtosecond visible pump-near IR dump-hyperspectral probe spectroscopy. The efficiency of excited state depletion is deduced from transient changes in absorption, recorded with and without stimulated emission pumping (SEP), as a function of the dump delay. The concomitant reduction of photocycle population is assessed by probing the "K" intermediate difference spectrum. Results show that the cross section for stimulating emission is nearly constant throughout the fluorescent state lifetime. Probing "K" demonstrates that dumping produces a proportionate reduction in photocycle yields. We conclude that, despite its nonexponential internal conversion (IC) kinetics, the fluorescent state in pHR constitutes a single intermediate in the photocycle. This contrasts with conclusions drawn from the study of primary events in the related chloride pump from Hb. salinarum (sHR), believed to produce the "K" intermediate from a distinct short-lived subpopulation in the excited state. Our discoveries concerning internal conversion dynamics in pHR are discussed in light of recent expectations for similar excited state dynamics in both proteins.

Relativistic configuration interaction calculation on the ground and excited states of iridium monoxide

International Nuclear Information System (INIS)

Suo, Bingbing; Yu, Yan-Mei; Han, Huixian

2015-01-01

We present the fully relativistic multi-reference configuration interaction calculations of the ground and low-lying excited electronic states of IrO for individual spin-orbit component. The lowest-lying state is calculated for Ω = 1/2, 3/2, 5/2, and 7/2 in order to clarify the ground state of IrO. Our calculation suggests that the ground state is of Ω = 1/2, which is highly mixed with 4 Σ − and 2 Π states in Λ − S notation. The two low-lying states 5/2 and 7/2 are nearly degenerate with the ground state and locate only 234 and 260 cm −1 above, respectively. The equilibrium bond length 1.712 Å and the harmonic vibrational frequency 903 cm −1 of the 5/2 state are close to the experimental measurement of 1.724 Å and 909 cm −1 , which suggests that the 5/2 state should be the low-lying state that contributes to the experimental spectra. Moreover, the electronic states that give rise to the observed transition bands are assigned for Ω = 5/2 and 7/2 in terms of the obtained excited energies and oscillator strengths

Holding molecular dications together in strong laser fields

International Nuclear Information System (INIS)

Guo Chunlei

2006-01-01

Metastable channel of doubly ionized carbon monoxide, CO 2+ , was scantly seen in previous strong-field experiments at the visible wavelength region, but was commonly observed using single high-energy photon or electron excitation. For the first time with near-IR ultrashort-pulse radiation, we observe an abundance of CO 2+ . We show that CO 2+ results from nonsequential double ionization, while its dissociation counterpart, C + +O + , results from sequential processes, and CO 2+ can be obtained through either single high-energy photon or electron excitation or multiphoton ionization with ultrashort pulses before a critical internuclear distance is reached. Our study demonstrates the experimental conditions to converge the outcomes from two vastly different regimes, namely, multiphoton excitation and ionization in strong fields and single high-energy photon or electron excitation and ionization in weak fields

Strong ligand field effects of blue phosphorescent Ir(III) complexes with phenylpyrazole and phosphines.

Science.gov (United States)

Park, Se Won; Ham, Ho Wan; Kim, Young Sik

2012-04-01

In the paper, we describe new Ir complexes for achieving efficient blue phosphorescence. New blue-emitting mixed-ligand Ir complexes comprising one cyclometalating, two phosphines trans to each other such as Ir(dppz)(PPh3)2(H)(L) (Ll= Cl, NCMe+, CN), [dppz = 3,5-Diphenylpyrazole] were synthesized and studied to tune the phosphorescence wavelength to the deep blue region and to enhance the luminescence efficiencies. To gain insight into the factors responsible for the emission color change and the variation of luminescence efficiency, we investigate the electron-withdrawing capabilities of ancillary ligands using DFT and TD-DFT calculations on the ground and excited states of the complexes. To achieve deep blue emission and increase the emission efficiency, (1) we substitute the phenyl group on the 3-position of the pyrazole ring that lowers the triplet energy enough that the quenching channel is not thermally accessible and (2) change the ancillary ligands coordinated to iridium atom to phosphine and cyano groups known as very strong field ligands. Their inclusion in the coordination sphere can increase the HOMO-LUMO gap to achieve the hypsochromic shift in emission color and lower the HOMO and LUMO energy level, which causes a large d-orbital energy splitting and avoids the quenching effect to improve the luminescence efficiency. The maximum emission spectra of Ir(dppz)(PPh3)2(H)(CI) and Ir(dppz)(PPh3)2(H)(CN) were in the ranges of 439, 432 nm, respectively.

Infrared reflection nebulae in Orion Molecular Cloud

International Nuclear Information System (INIS)

Pendleton, Y.; Werner, M.W.; Capps, R.; Lester, D.; Hawaii Univ., Honolulu; Texas Univ., Austin)

1986-01-01

New observations of Orion Molecular Cloud 2 have been made from 1 to 100 microns using the NASA Infrared Telescope Facility and the Kuiper Airborne Observatory. An extensive program of polarimetry, photometry, and spectrophotometry has shown that the extended emission regions associated with two of the previously known near-infrared sources, IRS 1 and IRS 4, are infrared reflection nebulae, and that the compact sources IRS 1 and IRS 4 are the main luminosity sources in the cloud. The constraints from the far-infrared observations and an analysis of the scattered light from the IRS 1 nebula show that OMC-2/IRS 1 can be characterized by L of 500 solar luminosities or less and T of roughly 1000 K. The near-infrared albedo of the grains in the IRS 1 nebula is greater than 0.08. 27 references

Vibrational spectroscopy of the electronically excited state. 4. Nanosecond and picosecond time-resolved resonance Raman spectroscopy of carotenoid excited states

International Nuclear Information System (INIS)

Dallinger, R.F.; Farquharson, S.; Woodruff, W.H.; Rodgers, M.A.J.

1981-01-01

Resonance Raman and electronic absorption spectra are reported for the S 0 and T 1 states of the carotenoids β-carotene, zeaxanthin, echinenone, canthaxanthin, dihydroxylycopene, astaxanthin, decapreno(C 50 )-β-carotene, β-apo-8'-carotenal, and ethyl β-apo-8'-carotenoate. The results reveal qualitatively similar ground-state spectra and similar frequency shifts in all observed resonance Raman modes between S 0 and T 1 , regardless of carotenoid structure. Examinations of the relationship of the putative C--C and C==C frequencies in S 0 and T 1 reveals anomalous shifts to lower frequency in the ''single-bond'' mode upon electronic excitation. These shifts may be due to molecular distortions in the excited state which force changes in molecular motions comprising the observed modes. However, another possibility requiring no distortion is that the interaction (off-diagonal) force constants connecting the C--C and C==C modes change sign upon electronic excitation. This latter phenomenon may provide a unitary explanation for the ''anomalous'' frequency shifts in the C--C and C==C modes, both in the T 1 states of carotenoids and in the S 1 states of simpler polyenes, without postulating large, unpredicted structural changes upon excitation or general errors in existing vibrational or theoretical analyses. Resonance Raman and absorbance studies with 35-ps time resolution suggest that S 1 lifetime (of the 1 B/sub u/ and/or the 1 A/sub g/* states) of β-carotene in benzene is less than 1 ps

The effect of excitation and preparation pulses on nonslice selective 2D UTE bicomponent analysis of bound and free water in cortical bone at 3T

Energy Technology Data Exchange (ETDEWEB)

Li, Shihong [Department of Radiology, University of California, San Diego, California 92103-8226 (United States); Department of Radiology, Hua Dong Hospital, Fudan University, Shanghai 200040 (China); Yancheng Medical College, Jiangsu (China); The First People' s Hospital of Yancheng City, Jiangsu 224005 (China); Chang, Eric Y.; Chung, Christine B. [VA San Diego Healthcare System, San Diego, California 92161 and Department of Radiology, University of California, San Diego, California 92103-8226 (United States); Bae, Won C.; Du, Jiang, E-mail: jiangdu@ucsd.edu [Department of Radiology, University of California, San Diego, California 92103-8226 (United States); Hua, Yanqing [Department of Radiology, Hua Dong Hospital, Fudan University, Shanghai 200040 (China); Zhou, Yi [The First People' s Hospital of Yancheng City, Jiangsu 224005 (China)

2014-02-15

Purpose: The purpose of this study was to investigate the effect of excitation, fat saturation, long T2 saturation, and adiabatic inversion pulses on ultrashort echo time (UTE) imaging with bicomponent analysis of bound and free water in cortical bone for potential applications in osteoporosis. Methods: Six bovine cortical bones and six human tibial midshaft samples were harvested for this study. Each bone sample was imaged with eight sequences using 2D UTE imaging at 3T with half and hard excitation pulses, without and with fat saturation, long T2 saturation, and adiabatic inversion recovery (IR) preparation pulses. Single- and bicomponent signal models were utilized to calculate the T2{sup *}s and/or relative fractions of short and long T2{sup *}s. Results: For all bone samples UTE T2{sup *} signal decay showed bicomponent behavior. A higher short T2{sup *} fraction was observed on UTE images with hard pulse excitation compared with half pulse excitation (75.6% vs 68.8% in bovine bone, 79.9% vs 73.2% in human bone). Fat saturation pulses slightly reduced the short T2{sup *} fraction relative to regular UTE sequences (5.0% and 2.0% reduction, respectively, with half and hard excitation pulses for bovine bone, 6.3% and 8.2% reduction, respectively, with half and hard excitation pulses for human bone). Long T2 saturation pulses significantly reduced the long T2{sup *} fraction relative to regular UTE sequence (18.9% and 17.2% reduction, respectively, with half and hard excitation pulses for bovine bone, 26.4% and 27.7% reduction, respectively, with half and hard excitation pulses for human bone). With IR-UTE preparation the long T2{sup *} components were significantly reduced relative to regular UTE sequence (75.3% and 66.4% reduction, respectively, with half and hard excitation pulses for bovine bone, 87.7% and 90.3% reduction, respectively, with half and hard excitation pulses for human bone). Conclusions: Bound and free water T2{sup *}s and relative fractions can

The effect of excitation and preparation pulses on nonslice selective 2D UTE bicomponent analysis of bound and free water in cortical bone at 3T

International Nuclear Information System (INIS)

Li, Shihong; Chang, Eric Y.; Chung, Christine B.; Bae, Won C.; Du, Jiang; Hua, Yanqing; Zhou, Yi

2014-01-01

Purpose: The purpose of this study was to investigate the effect of excitation, fat saturation, long T2 saturation, and adiabatic inversion pulses on ultrashort echo time (UTE) imaging with bicomponent analysis of bound and free water in cortical bone for potential applications in osteoporosis. Methods: Six bovine cortical bones and six human tibial midshaft samples were harvested for this study. Each bone sample was imaged with eight sequences using 2D UTE imaging at 3T with half and hard excitation pulses, without and with fat saturation, long T2 saturation, and adiabatic inversion recovery (IR) preparation pulses. Single- and bicomponent signal models were utilized to calculate the T2 * s and/or relative fractions of short and long T2 * s. Results: For all bone samples UTE T2 * signal decay showed bicomponent behavior. A higher short T2 * fraction was observed on UTE images with hard pulse excitation compared with half pulse excitation (75.6% vs 68.8% in bovine bone, 79.9% vs 73.2% in human bone). Fat saturation pulses slightly reduced the short T2 * fraction relative to regular UTE sequences (5.0% and 2.0% reduction, respectively, with half and hard excitation pulses for bovine bone, 6.3% and 8.2% reduction, respectively, with half and hard excitation pulses for human bone). Long T2 saturation pulses significantly reduced the long T2 * fraction relative to regular UTE sequence (18.9% and 17.2% reduction, respectively, with half and hard excitation pulses for bovine bone, 26.4% and 27.7% reduction, respectively, with half and hard excitation pulses for human bone). With IR-UTE preparation the long T2 * components were significantly reduced relative to regular UTE sequence (75.3% and 66.4% reduction, respectively, with half and hard excitation pulses for bovine bone, 87.7% and 90.3% reduction, respectively, with half and hard excitation pulses for human bone). Conclusions: Bound and free water T2 * s and relative fractions can be assessed using UTE bicomponent

Molecular spinning by a chiral train of short laser pulses

Science.gov (United States)

Floß, Johannes; Averbukh, Ilya Sh.

2012-12-01

We provide a detailed theoretical analysis of molecular rotational excitation by a chiral pulse train, a sequence of linearly polarized pulses with the polarization direction rotating from pulse to pulse by a controllable angle. Molecular rotation with a preferential rotational sense (clockwise or counterclockwise) can be excited by this scheme. We show that the directionality of the rotation is caused by quantum interference of different excitation pathways. The chiral pulse train is capable of selective excitation of molecular isotopologs and nuclear spin isomers in a mixture. We demonstrate this using 14N2 and 15N2 as examples for isotopologs and para- and ortho-nitrogen as examples for nuclear-spin isomers.

A density functional study on adsorption and dissociation of O 2 on Ir(1 0 0) surface

Science.gov (United States)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2011-06-01

The adsorption and the reaction barrier for the dissociation of O 2 on Ir(1 0 0) surface are studied using periodic self-consistent density functional theory (DFT) calculations. Dissociative adsorption is found to be energetically more favorable compared to molecular adsorption. Parallel approaches Prl1 and Prl2 on a hollow site with the same adsorption energy of -3.93 eV for both of them are found to have the most energetically preferred sites of adsorptions among all the studied cases. Hybridization between p-O 2 and d-metal orbitals is responsible for the dissociative adsorption. The minimum energy path is determined by using the nudge elastic band method (NEB). We found that the dissociation occurs immediately and very early in the dissociation path with a small activation barrier (0.26 eV), which means that molecular adsorption of O 2 on Ir(1 0 0) surface occurs at very low temperatures; this is consistent with previous experimental and theoretical studies on Ir surfaces.

Diamond-like nanoparticles influence on flavonoids transport: molecular modelling

Science.gov (United States)

Plastun, Inna L.; Agandeeva, Ksenia E.; Bokarev, Andrey N.; Zenkin, Nikita S.

2017-03-01

Intermolecular interaction of diamond-like nanoparticles and flavonoids is investigated by numerical simulation. Using molecular modelling by the density functional theory method, we analyze hydrogen bonds formation and their influence on IR - spectra and structure of molecular complex which is formed due to interaction between flavonoids and nanodiamonds surrounded with carboxylic groups. Enriched adamantane (1,3,5,7 - adamantanetetracarboxylic acid) is used as an example of diamond-like nanoparticles. Intermolecular forces and structure of hydrogen bonds are investigated. IR - spectra and structure parameters of quercetin - adamantanetetracarboxylic acid molecular complex are obtained by numerical simulation using the Gaussian software complex. Received data coincide well with experimental results. Intermolecular interactions and hydrogen bonding structure in the obtained molecular complex are examined. Possibilities of flavonoids interaction with DNA at the molecular level are also considered.

Observation of a Slater-type metal-to-insulator transition in Sr$_2$IrO$_4$ from time-resolved photo-carrier dynamics

OpenAIRE

Hsieh, D.; Mahmood, F.; Torchinsky, D. H.; Cao, G.; Gedik, N.

2012-01-01

We perform a time-resolved optical study of Sr$_2$IrO$_4$ to understand the influence of magnetic ordering on the low energy electronic structure of a strongly spin-orbit coupled $J_{eff}$=1/2 Mott insulator. By studying the recovery dynamics of photo-carriers excited across the Mott gap, we find that upon cooling through the N\\'{e}el temperature $T_N$ the system evolves continuously from a metal-like phase with fast ($\\sim$50 fs) and excitation density independent relaxation dynamics to a ga...

Monitoring voltage-dependent charge displacement of Shaker B-IR K+ ion channels using radio frequency interrogation.

Directory of Open Access Journals (Sweden)

Sameera Dharia

2011-02-01

Full Text Available Here we introduce a new technique that probes voltage-dependent charge displacements of excitable membrane-bound proteins using extracellularly applied radio frequency (RF, 500 kHz electric fields. Xenopus oocytes were used as a model cell for these experiments, and were injected with cRNA encoding Shaker B-IR (ShB-IR K(+ ion channels to express large densities of this protein in the oocyte membranes. Two-electrode voltage clamp (TEVC was applied to command whole-cell membrane potential and to measure channel-dependent membrane currents. Simultaneously, RF electric fields were applied to perturb the membrane potential about the TEVC level and to measure voltage-dependent RF displacement currents. ShB-IR expressing oocytes showed significantly larger changes in RF displacement currents upon membrane depolarization than control oocytes. Voltage-dependent changes in RF displacement currents further increased in ShB-IR expressing oocytes after ∼120 µM Cu(2+ addition to the external bath. Cu(2+ is known to bind to the ShB-IR ion channel and inhibit Shaker K(+ conductance, indicating that changes in the RF displacement current reported here were associated with RF vibration of the Cu(2+-linked mobile domain of the ShB-IR protein. Results demonstrate the use of extracellular RF electrodes to interrogate voltage-dependent movement of charged mobile protein domains--capabilities that might enable detection of small changes in charge distribution associated with integral membrane protein conformation and/or drug-protein interactions.

Monitoring voltage-dependent charge displacement of Shaker B-IR K+ ion channels using radio frequency interrogation.

Science.gov (United States)

Dharia, Sameera; Rabbitt, Richard D

2011-02-28

Here we introduce a new technique that probes voltage-dependent charge displacements of excitable membrane-bound proteins using extracellularly applied radio frequency (RF, 500 kHz) electric fields. Xenopus oocytes were used as a model cell for these experiments, and were injected with cRNA encoding Shaker B-IR (ShB-IR) K(+) ion channels to express large densities of this protein in the oocyte membranes. Two-electrode voltage clamp (TEVC) was applied to command whole-cell membrane potential and to measure channel-dependent membrane currents. Simultaneously, RF electric fields were applied to perturb the membrane potential about the TEVC level and to measure voltage-dependent RF displacement currents. ShB-IR expressing oocytes showed significantly larger changes in RF displacement currents upon membrane depolarization than control oocytes. Voltage-dependent changes in RF displacement currents further increased in ShB-IR expressing oocytes after ∼120 µM Cu(2+) addition to the external bath. Cu(2+) is known to bind to the ShB-IR ion channel and inhibit Shaker K(+) conductance, indicating that changes in the RF displacement current reported here were associated with RF vibration of the Cu(2+)-linked mobile domain of the ShB-IR protein. Results demonstrate the use of extracellular RF electrodes to interrogate voltage-dependent movement of charged mobile protein domains--capabilities that might enable detection of small changes in charge distribution associated with integral membrane protein conformation and/or drug-protein interactions.

Spectroscopic investigation (FT-IR and FT-Raman), vibrational assignments, HOMO-LUMO analysis and molecular docking study of 1-hydroxy-4,5,8-tris(4-methoxyphenyl) anthraquinone

Science.gov (United States)

Renjith, R.; Sheena Mary, Y.; Tresa Varghese, Hema; Yohannan Panicker, C.; Thiemann, Thies; Shereef, Anas; Al-Saadi, Abdulaziz A.

2015-12-01

FT-IR and FT-Raman spectra of 1-hydroxy-4,5,8-tris(4-methoxyphenyl)anthraquinone were recorded and analyzed. The vibrational wavenumbers were computed using DFT quantum chemical calculations. The data obtained from wavenumber calculations were used to assign the vibrational bands obtained experimentally. A detailed molecular picture of the title compound and its interactions were obtained from NBO analysis. From the MEP plot it is clear that the negative electrostatic potential regions are mainly localized over carbonyl group. There is some evidence of a region of negative electrostatic potential due to π-electron density of the benzo groups. Molecular docking study shows that methoxy groups attached to the phenyl rings and hydroxyl group are crucial for binding and the title compound might exhibit inhibitory activity against PI3K and may act as an anti-neoplastic agent.

Study of micro-phase separation of two polystyrene-based copolymer mixture using the combination of PALS and FT-IR

International Nuclear Information System (INIS)

Jiang, Z.Y.; Jiang, X.Q.; Yang, Y.X.; Huang, Y.J.; Huang, H.B.; Hsia, Y.F.

2005-01-01

Positron annihilation lifetime (PAL) spectroscopy, Fourier transform infrared (FT-IR) and differential scanning calorimetry (DSC) have been applied to study the micro-phase separation in the blends of poly(styrene-co-methylmethacrylate) (SMMA) copolymer and poly(styrene-co-maleic anhydride) (SMA) copolymer. The DSC results indicate that the SMA/SMMA blends are miscible and weak intermolecular interactions exist between SMA and SMMA. The strength of intermolecular interactions to some degree exhibits somewhat non-monotonic variation with increasing of SMA component in the blends. The results of PAL measurement present the blend containing 20 wt% SMA is phase-separated in molecular level, which is interpreted by the results of FT-IR analysis. It was concluded that it is helpful to study the miscibility of polymer blends in molecular level by means of PAL method, accompanied with the requisite measurement of DSC and FT-IR

On the nature of intramolecular vibrational energy transfer in dense molecular environments

Energy Technology Data Exchange (ETDEWEB)

Benten, Rebekka S. von [Institut fuer Physikalische Chemie der Universitaet Goettingen, Tammannstrasse 6, D-37077 Goettingen (Germany); Abel, Bernd, E-mail: Bernd.Abel@uni-lepzig.de [Wilhelm-Ostwald-Institut fuer Physikalische und Theoretische Chemie, Universitaet Leipzig, Linne-Strasse 2, D-04103 Leipzig (Germany)

2010-12-09

Graphical abstract: Mechanisms of IVR in multi-tiers of intramolecular energy levels in different molecular environments are investigated. - Abstract: Transient femtosecond-IR-pump-UV-absorption probe-spectroscopy has been employed to shed light on the nature of intramolecular vibrational energy transfer (IVR) in dense molecular environments ranging from the diluted gas phase to the liquid. A general feature in our experiments and those of others is that IVR proceeds via multiple timescales if overtones or combination vibrations of high frequency modes are excited. It has been found that collisions enhance IVR if its (slower) timescales can compete with collisions. This enhancement is, however, much more weaker and rather inefficient as opposed to the effect of collisions on intermolecular energy transfer which is well known. In a series of experiments we found that IVR depends not significantly on the average energy transferred in a collision but rather on the number of collisions. The collisions are much less efficient in affecting IVR than VET. We conclude that collision induced broadening of vibrational energy levels reduces the energy gaps and enhances existing couplings between tiers. The present results are an important step forward to rationalize and understand apparently different and not consistent results from different groups on different molecular systems between gas and liquid phases.

Plume characteristics and dynamics of UV and IR laser-desorbed oligonucleotides.

Science.gov (United States)

Merrigan, Tony L; Timson, David J; Hunniford, C Adam; Catney, Martin; McCullough, Robert W

2012-05-01

Laser desorption of dye-tagged oligonucleotides was studied using laser-induced fluorescence imaging. Desorption with ultra violet (UV) and infra-red (IR) lasers resulted in forward directed plumes of molecules. In the case of UV desorption, the initial shot desorbed approximately seven-fold more material than subsequent shots. In contrast, the initial shot in IR desorption resulted in the ejection of less material compared to subsequent shots and these plumes had a component directed along the path of the laser. Thermal equilibrium of the molecules in the plume was achieved after approximately 25 μs with a spread in molecular temperature which was described by a modified Maxwell-Boltzmann equation. Copyright © 2012 Elsevier B.V. All rights reserved.

IR spectral analysis for the diagnostics of crust earthquake precursors

Science.gov (United States)

Umarkhodgaev, R. M.; Liperovsky, V. A.; Mikhailin, V. V.; Meister, C.-V.; Naumov, D. Ju

2012-04-01

In regions of future earthquakes, a few days before the seismic shock, the emanation of radon and hydrogen is being observed, which causes clouds of increased ionisation in the atmosphere. In the present work the possible diagnostics of these clouds using infrared (IR) spectroscopy is considered, which may be important and useful for the general geophysical system of earthquake prediction and the observation of industrial emissions of radioactive materials into the atmosphere. Some possible physical processes are analysed, which cause, under the condition of additional ionisation in a pre-breakdown electrical field, emissions in the IR interval. In doing so, the transparency region of the IR spectrum at wavelengths of 7-15 μm is taken into account. This transparency region corresponds to spectral lines of small atmospheric constituents like CH4, CO2, N2O, NO2, NO, and O3. The possible intensities of the IR emissions observable in laboratories and in nature are estimated. The acceleration process of the electrons in the pre-breakdown electrical field before its adhesion to the molecules is analysed. The laboratory equipment for the investigation of the IR absorption spectrum is constructed for the cases of normal and decreased atmospheric pressures. The syntheses of ozone and nitrous oxides are performed in the barrier discharge. It is studied if the products of the syntheses may be used to model atmospheric processes where these components take part. Spectra of products of the syntheses in the wavelength region of 2-10 μm are observed and analysed. A device is created for the syntheses and accumulation of nitrous oxides. Experiments to observe the IR-spectra of ozone and nitrous oxides during the syntheses and during the further evolution of these molecules are performed. For the earthquake prediction, practically, the investigation of emission spectra is most important, but during the laboratory experiments, the radiation of the excited molecules is shifted by a

Dissociative photoionization of molecular hydrogen. A joint experimental and theoretical study of the electron-electron correlations induced by XUV photoionization and nuclear dynamics on IR-laser dressed transition states

Energy Technology Data Exchange (ETDEWEB)

Fischer, Andreas

2015-01-13

In this thesis, the dissociative single-ionization of molecular hydrogen is investigated in a kinematically complete experiment by employing extreme ultraviolet attosecond pulse trains and infrared femtosecond laser pulses. Induced by the absorption of a single XUV photon, a pronounced energy-dependent asymmetry of the relative emission direction of the photoelectron and the ion is observed. The asymmetry pattern is explained in terms of an interference of two ionization pathways involving a doubly-excited state. This interpretation is validated by a semi-classical model which only takes the nuclear motion into account. Using this model and the observed asymmetry, it is furthermore possible to disentangle the two dissociation pathways which allows for the determination of the autoionization lifetime of the contributing doubly-excited state as a function of the internuclear distance. Moreover, using a pump-probe experiment the dissociation dynamics of molecular hydrogen is investigated. A time-delay dependent momentum distribution of the fragments is observed. With a combined quantum mechanical and semi-classical approach the mechanism giving rise to the observed time-dependence is identified in terms of an intuitive elevator mechanism.

Wobbling excitation of triaxial nuclear molecule 28Si – 28Si

International Nuclear Information System (INIS)

Uegaki, E; Abe, Y

2013-01-01

High-spin resonances observed in the 28 Si + 28 Si collisions are investigated with a molecular model. At high spins, a stable dinuclear configuration is found to be an equator-equator touching one. Since the E-E configuration is slightly triaxial, rotations of the total system induce mixing of K quantum numbers, called wobbling motion, which clearly explains the particle-γ angular correlations observed as well as the disalignments in a simple and natural way. Furthermore, predictions are given for the angular correlations of the wobbling excited states. The first excited state of wobbling shows strong alignments, which is quite different from the molecular ground state.

Charge transfer excitations from exact and approximate ensemble Kohn-Sham theory

Science.gov (United States)

Gould, Tim; Kronik, Leeor; Pittalis, Stefano

2018-05-01

By studying the lowest excitations of an exactly solvable one-dimensional soft-Coulomb molecular model, we show that components of Kohn-Sham ensembles can be used to describe charge transfer processes. Furthermore, we compute the approximate excitation energies obtained by using the exact ensemble densities in the recently formulated ensemble Hartree-exchange theory [T. Gould and S. Pittalis, Phys. Rev. Lett. 119, 243001 (2017)]. Remarkably, our results show that triplet excitations are accurately reproduced across a dissociation curve in all cases tested, even in systems where ground state energies are poor due to strong static correlations. Singlet excitations exhibit larger deviations from exact results but are still reproduced semi-quantitatively.

Spin orientations of the spin-half Ir(4+) ions in Sr3NiIrO6, Sr2IrO4, and Na2IrO3: Density functional, perturbation theory, and Madelung potential analyses.

Science.gov (United States)

Gordon, Elijah E; Xiang, Hongjun; Köhler, Jürgen; Whangbo, Myung-Hwan

2016-03-21

The spins of the low-spin Ir(4+) (S = 1/2, d(5)) ions at the octahedral sites of the oxides Sr3NiIrO6, Sr2IrO4, and Na2IrO3 exhibit preferred orientations with respect to their IrO6 octahedra. We evaluated the magnetic anisotropies of these S = 1/2 ions on the basis of density functional theory (DFT) calculations including spin-orbit coupling (SOC), and probed their origin by performing perturbation theory analyses with SOC as perturbation within the LS coupling scheme. The observed spin orientations of Sr3NiIrO6 and Sr2IrO4 are correctly predicted by DFT calculations, and are accounted for by the perturbation theory analysis. As for the spin orientation of Na2IrO3, both experimental studies and DFT calculations have not been unequivocal. Our analysis reveals that the Ir(4+) spin orientation of Na2IrO3 should have nonzero components along the c- and a-axis directions. The spin orientations determined by DFT calculations are sensitive to the accuracy of the crystal structures employed, which is explained by perturbation theory analyses when interactions between adjacent Ir(4+) ions are taken into consideration. There are indications implying that the 5d electrons of Na2IrO3 are less strongly localized compared with those of Sr3NiIrO6 and Sr2IrO4. This implication was confirmed by showing that the Madelung potentials of the Ir(4+) ions are less negative in Na2IrO3 than in Sr3NiIrO6 and Sr2IrO4. Most transition-metal S = 1/2 ions do have magnetic anisotropies because the SOC induces interactions among their crystal-field split d-states, and the associated mixing of the states modifies only the orbital parts of the states. This finding cannot be mimicked by a spin Hamiltonian because this model Hamiltonian lacks the orbital degree of freedom, thereby leading to the spin-half syndrome. The spin-orbital entanglement for the 5d spin-half ions Ir(4+) is not as strong as has been assumed.

MicroRNA-145 suppresses hepatocellular carcinoma by targeting IRS1 and its downstream Akt signaling

Energy Technology Data Exchange (ETDEWEB)

Wang, Yelin [Department of Anesthesiology, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China); Key Laboratory of Combined Multi-organ Transplantation, Ministry of Public Health, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China); Hu, Chen; Cheng, Jun [Department of Surgery, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China); Key Laboratory of Combined Multi-organ Transplantation, Ministry of Public Health, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China); Chen, Binquan [Department of Anesthesiology, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China); Ke, Qinghong; Lv, Zhen; Wu, Jian [Department of Surgery, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China); Key Laboratory of Combined Multi-organ Transplantation, Ministry of Public Health, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China); Zhou, Yanfeng, E-mail: zyfhdj@yahoo.com [Department of Anesthesiology, The First Affiliated Hospital, School of Medicine, Zhejiang University, Hangzhou (China)

2014-04-18

Highlights: • MiR-145 expression is down-regulated in HCC tissues and inversely related with IRS1 levels. • MiR-145 directly targets IRS1 in HCC cells. • Restored expression of miR-145 suppressed HCC cell proliferation and growth. • MiR-145 induced IRS1 under-expression potentially reduced downstream AKT signaling. - Abstract: Accumulating evidences have proved that dysregulation of microRNAs (miRNAs) is involved in cancer initiation and progression. In this study, we showed that miRNA-145 level was significantly decreased in hepatocellular cancer (HCC) tissues and cell lines, and its low expression was inversely associated with the abundance of insulin receptor substrate 1 (IRS1), a key mediator in oncogenic insulin-like growth factor (IGF) signaling. We verified IRS1 as a direct target of miR-145 using Western blotting and luciferase reporter assay. Further, the restoration of miR-145 in HCC cell lines suppressed cancer cell growth, owing to down-regulated IRS1 expression and its downstream Akt/FOXO1 signaling. Our results demonstrated that miR-145 could inhibit HCC through targeting IRS1 and its downstream signaling, implicating the loss of miR-145 regulation may be a potential molecular mechanism causing aberrant oncogenic signaling in HCC.

Choice of Eye-Safe Radiation Wavelength in UV and Near IR Spectral Bands for Remote Sensing

Directory of Open Access Journals (Sweden)

M. L. Belov

2016-01-01

Full Text Available The introduction of laser remote sensing systems carries a particular risk to the human’s sense of vision. A structure of the eye, and especially the retina, is the main critical organ as related to the laser radiation.The work uses the optical models of the atmosphere, correctly working in both the UV and the near-IR band, to select the eye-safe radiation wavelengths in the UV (0.355 m and near-IR (~ 1.54 and ~ 2 m spectral bands from the point of view of recorded lidar signal value to fulfill the tasks of laser sensing the natural formations and laser aerosol sensing in the atmosphere.It is shown that the remote sensing lasers with appropriate characteristics can be selected both in the UV band (at a wavelength of 0.355 μm and in the near-IR band (at wavelengths of 1.54 ~ or ~ 2 μm.Molecular scattering has its maximum (for the selected wavelength at a wavelength of 0.355 μm in the UV band, and the minimum at the wavelengths of 1.54 and 2.09 μm in the near -IR band. The main contribution to the molecular absorption at a wavelength of 0.355 μm is made by ozone. In the near-IR spectral band the radiation is absorbed due to water vapor and carbon dioxide.Calculations show that the total effect of the molecular absorption and scattering has no influence on radiation transmission for both the wavelength of 0.355 μm in the UV band, and the wavelengths of 1.54 and 2.09 μm in the near-IR band for sensing trails ~ 1 km.One of the main factors of laser radiation attenuation in the Earth's atmosphere is radiation scattering by aerosol particles.The results of calculations at wavelengths of 0.355 μm, 1.54 μm and 2.09 μm for the several models of the atmosphere show that a choice of the most effective (in terms of the recorded signal of lidar and eye-safe radiation wavelength depends strongly on the task of sensing.To fulfill the task of laser sensing the natural formations, among the eye-safe wavelengths there is one significantly advantageous

Luminescent chiral ionic Ir(III) complexes: Synthesis and photophysical properties

Energy Technology Data Exchange (ETDEWEB)

Ricciardi, Loredana, E-mail: loredana.ricciardi@unical.it [CNR NANOTEC-Istituto di Nanotecnologia U.O.S. Cosenza, 87036 Arcavacata di Rende (CS) (Italy); La Deda, Massimo; Ionescu, Andreea; Godbert, Nicolas; Aiello, Iolinda; Ghedini, Mauro [MAT-INLAB (Laboratorio di Materiali Molecolari Inorganici), LASCAMM and CR INSTM, Unità INSTM della Calabria, Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, 87036 Arcavacata di Rende (CS) (Italy); Fusè, Marco, E-mail: marco.fuse@unimi.it [Dipartimento di Scienze Farmaceutiche, Università di Milano, Via Golgi 19, 20133 Milano (Italy); Rimoldi, Isabella; Cesarotti, Edoardo [Dipartimento di Scienze Farmaceutiche, Università di Milano, Via Golgi 19, 20133 Milano (Italy)

2016-02-15

Three homologous series of luminescent octahedral ionic Ir(III) complexes (1–12) with a dual stereogenic center of general formula {sup Δ,Λ} {sup (R,S)}[(ppy){sub 2}Ir(R-campy)]X, where ppy=2-phenylpyridine, R-campy=2-methyl-5,6,7,8-tetrahydroquinolin-8-amine (Me-campy) or 8-amino-5,6,7,8-tetrahydroquinolines (H-campy) and as counterions X{sup −}=Cl{sup −} or CH{sub 3}COO{sup −} have been synthesized and characterized. The NMR characterization of each complex highlighted the diastereoisomeric purity and the absolute configuration has been confirmed by Electronic Circular Dichroism spectroscopy. The absorption and the luminescence properties of the compounds in solution and in solid state have been investigated by UV–vis, steady-state emission and time-correlated single-photon counting spectroscopy. The obtained results from the 12 compounds highlight the difficult to correlate photophysical properties in solution to the stereochemistry, while excited states decay studies of the solid state samples indicate a correlation between photophysics and packing mode which is affected by the different stereochemistry. - Highlights: • Luminescent chiral ionic Ir(III) complexes have been synthesized and characterized. • Presence in the same structure of two stereogenic centers. • Use of camphorsulfonate as resolving anion to obtain enantiomerically pure samples. • Stereoisomers produce aggregates with different emitting properties. • Lifetimes from solid samples show the presence of AIPE.

Rutile IrO2/TiO2 superlattices: A hyperconnected analog to the Ruddelsden-Popper structure

Science.gov (United States)

Kawasaki, Jason K.; Baek, David; Paik, Hanjong; Nair, Hari P.; Kourkoutis, Lena F.; Schlom, Darrell G.; Shen, Kyle M.

2018-05-01

Dimensionality and connectivity among octahedra play important roles in determining the properties, electronic structure, and phase transitions of transition-metal oxides. Here we demonstrate the epitaxial growth of (110)-oriented alternating layers of IrO2 and TiO2, both of which have the rutile structure. These (IrO2)n/(TiO2)2 superlattices consist of IrO6 and TiO6 octahedra tiled in a hyperconnected, edge- and corner-sharing network. Despite the large lattice mismatch between constituent layers (Δ d∥=-2.1 % and Δ c =+6.6 % ), our reactive molecular-beam epitaxy-grown superlattices show high structural quality as determined by x-ray diffraction and sharp interfaces as observed by transmission electron microscopy. The large strain at the interface is accommodated by an ordered interfacial reconstruction. The superlattices show persistent metallicity down to n =3 atomic layers, and angle-resolved photoemission spectroscopy measurements reveal quantized sub-bands with signatures of IrO2-IrO2 interlayer coupling.

Sum-rule analysis of long-wavelength excitations in electron liquids

International Nuclear Information System (INIS)

Ichimaru, Setsuo; Totsuji, Hiroo; Tange, Toshio; Pines, D.

1975-01-01

The properties of the plasma oscillations, the single-particle excitations and the collisional excitations in the classical one-component plasma are investigated in the long-wave-length domain with the aid of moment sum rules. The frequency moments of the dynamic form factor are calculated up to that term which involves the ternary correlation function. The dispersion in the plasma-wave frequency and the strengths of the single-particle and collisional excitations are computed over the thermodynamically stable domain of the plasma parameter, epsilon<=10. It is emphasized that inclusion of the collisional excitations plays a vital part in satisfying various moment-sum rules and in securing agreement with known boundary conditions such as the Vlasov description and molecular-dynamics computations. (auth.)

Theoretical study on molecular packing and electronic structure of bi-1,3,4-oxadiazole derivatives

KAUST Repository

Wang, Haitao; Bai, Fuquan; Jia, Xiaoshi; Cao, Di; Ravva, Mahesh Kumar; Bredas, Jean-Luc; Qu, Songnan; Bai, Binglian; Zhang, Hongxing; Li, Min

2014-01-01

The molecular aggregation structure of 5,5′-bis(naphthalen-2-yl)-2,2′-bi(1,3,4-oxadiazole) (BOXD-NP) was studied by computing the intermolecular interaction potential energy surface (PES) at density functional theory level based on a dimer model. All B3LYP, CAM-B3LYP and M062x functionals can yield a reliable isolated molecular geometry. The conformation of BOXD-NP obtained with all methods is perfectly planar, indicating good conjugation ability between oxadiazole and naphthalene rings. The vibrational frequencies of BOXD-NP were also calculated using the B3LYP/6-311+G∗∗ method, which showed great consistency with the experimental observations and makes the assignments of the IR spectra more solid. It was revealed that the lowest excited state of BOXD-NP should be assigned as a highly allowed π-π∗ state by TD-DFT calculation. Considering the non-covalent interactions in molecular aggregates, the M062x functional was applied in the construction of the PES. Besides the packing structure found in the crystals, PES also predicted several stable structures, indicating that PES has great ability in guiding molecular self-assembly. Symmetry Adapted Perturbation Theory (SAPT) analysis on these energy-minimum molecular stacking structures revealed that London dispersion forces are the strongest attractive component in the binding. This journal is

Ab Initio molecular dynamics with excited electrons

NARCIS (Netherlands)

Alavi, A.; Kohanoff, J.; Parrinello, M.; Frenkel, D.

1994-01-01

A method to do ab initio molecular dynamics suitable for metallic and electronically hot systems is described. It is based on a density functional which is costationary with the finite-temperature functional of Mermin, with state being included with possibly fractional occupation numbers.

Low-lying excited states by constrained DFT

Science.gov (United States)

Ramos, Pablo; Pavanello, Michele

2018-04-01

Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, Nc, in the virtual space of a reference set of occupied orbitals. By imposing this population to be Nc = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H3) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

Nuclear excited power generation system

International Nuclear Information System (INIS)

Parker, R.Z.; Cox, J.D.

1989-01-01

A power generation system is described, comprising: a gaseous core nuclear reactor; means for passing helium through the reactor, the helium being excited and forming alpha particles by high frequency radiation from the core of the gaseous core nuclear reactor; a reaction chamber; means for coupling chlorine and hydrogen to the reaction chamber, the helium and alpha particles energizing the chlorine and hydrogen to form a high temperature, high pressure hydrogen chloride plasma; means for converting the plasma to electromechanical energy; means for coupling the helium back to the gaseous core nuclear reactor; and means for disassociating the hydrogen chloride to form molecular hydrogen and chlorine, to be coupled back to the reaction chamber in a closed loop. The patent also describes a power generation system comprising: a gaseous core nuclear reactor; means for passing hydrogen through the reactor, the hydrogen being excited by high frequency radiation from the core; means for coupling chlorine to a reaction chamber, the hydrogen energizing the chlorine in the chamber to form a high temperature, high pressure hydrogen chloride plasma; means for converting the plasma to electromechanical energy; means for disassociating the hydrogen chloride to form molecular hydrogen and chlorine, and means for coupling the hydrogen back to the gaseous core nuclear reactor in a closed loop

Fluorescent vibration-rotation excitation of cometary C2

NARCIS (Netherlands)

Gredel, R.; Dishoeck, van E.F.; Black, J.H.

1989-01-01

The statistical equilibrium equations that determine the population densities of the energy levels in cometary C2 molecules due to fluorescent excitation are examined in detail. The adopted model and molecular parameters are discussed, and a theoretical estimate is made of the two intercombination

Spectroscopic [FT-IR and FT-Raman] and theoretical [UV-Visible and NMR] analysis on α-Methylstyrene by DFT calculations.

Science.gov (United States)

Karthikeyan, N; Joseph Prince, J; Ramalingam, S; Periandy, S

2015-05-15

In the present research work, the FT-IR, FT-Raman and (13)C and (1)H NMR spectra of the α-Methylstyrene were recorded. The observed fundamental frequencies in finger print as well as functional group regions were assigned according to their uniqueness region. The Gaussian computational calculations are carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results were tabulated. The impact of the presence of vinyl group in phenyl structure of the compound is investigated. The modified vibrational pattern of the molecule associated vinyl group was analyzed. Moreover, (13)C NMR and (1)H NMR were calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts linked to TMS were compared. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies were carried out. The kubo gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The NLO properties related to Polarizability and hyperpolarizability based on the finite-field approach were also discussed. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Nonlinear excitations in biomolecules

International Nuclear Information System (INIS)

Peyrard, M.

1995-01-01

The aim of the workshop entitled ''Nonlinear Excitations in Biomolecules'' is to attempt to bridge the gap between the physicists and biologists communities which is mainly due to language and cultural barriers. The progress of nonlinear science in the last few decades which have shown that the combination of nonlinearity, which characterize most biological phenomena, and cooperative effects in a system having a large number of degrees of freedom, can give rise to coherent excitations with remarkable properties. New concepts, such as solitons nd nonlinear energy localisation have become familiar to physicists and applied mathematicians. It is thus tempting to make an analogy between these coherent excitations and the exceptional stability of some biological processes, such as for instance DNA transcription, which require the coordination of many events in the ever changing environment of a cell. Physicists are now invoking nonlinear excitations to describe and explain many bio-molecular processes while biologists often doubt that the seemingly infinite variety of phenomena that they are attempting to classify can be reduced to such simple concepts. A large part of the meeting is devoted to tutorial lectures rather than to latest research results. The book provides a pedagogical introduction to the two topics forming the backbone of the meeting: the theory of nonlinear excitations and solitons, and their application in biology; and the structure and function of biomolecules, as well as energy and charge transport in biophysics. In order to emphasize the link between physics and biology, the volume is not divided along these two topics but according to biological subjects. Each chapter starts with a short introduction attempting to help the reader to find his way among the contributions and point out the connection between them. 23 lectures over the 32 presented have been selected and refers to quantum properties of macro-molecules. (J.S.)

Pulsed infrared radiation excites cultured neonatal spiral and vestibular ganglion neurons by modulating mitochondrial calcium cycling.

Science.gov (United States)

Lumbreras, Vicente; Bas, Esperanza; Gupta, Chhavi; Rajguru, Suhrud M

2014-09-15

Cochlear implants are currently the most effective solution for profound sensorineural hearing loss, and vestibular prostheses are under development to treat bilateral vestibulopathies. Electrical current spread in these neuroprostheses limits channel independence and, in some cases, may impair their performance. In comparison, optical stimuli that are spatially confined may result in a significant functional improvement. Pulsed infrared radiation (IR) has previously been shown to elicit responses in neurons. This study analyzes the response of neonatal rat spiral and vestibular ganglion neurons in vitro to IR (wavelength = 1,863 nm) using Ca(2+) imaging. Both types of neurons responded consistently with robust intracellular Ca(2+) ([Ca(2+)]i) transients that matched the low-frequency IR pulses applied (4 ms, 0.25-1 pps). Radiant exposures of ∼637 mJ/cm(2) resulted in continual neuronal activation. Temperature or [Ca(2+)] variations in the media did not alter the IR-evoked transients, ruling out extracellular Ca(2+) involvement or primary mediation by thermal effects on the plasma membrane. While blockage of Na(+), K(+), and Ca(2+) plasma membrane channels did not alter the IR-evoked response, blocking of mitochondrial Ca(2+) cycling with CGP-37157 or ruthenium red reversibly inhibited the IR-evoked [Ca(2+)]i transients. Additionally, the magnitude of the IR-evoked transients was dependent on ryanodine and cyclopiazonic acid-dependent Ca(2+) release. These results suggest that IR modulation of intracellular calcium cycling contributes to stimulation of spiral and vestibular ganglion neurons. As a whole, the results suggest selective excitation of neurons in the IR beam path and the potential of IR stimulation in future auditory and vestibular prostheses. Copyright © 2014 the American Physiological Society.

A new Density Functional Theory (DFT) based method for supporting the assignment of vibrational signatures of mannan and cellulose—Analysis of palm kernel cake hydrolysis by ATR-FT-IR spectroscopy as a case study

DEFF Research Database (Denmark)

Barsberg, Søren Talbro; Sanadi, Anand Ramesh; Jørgensen, Henning

2011-01-01

Attenuated Total Reflectance (ATR) FT-IR spectroscopy gives in situ information on molecular concentration, organization and interactions in plant cell walls. We demonstrate its potential for further developments by a case study which combines ATR-FT-IR spectroscopy with a recently published DFT...... a decreasing degree of polymerization to be a plausible cause, although others may interfere. Keywords: Cellulose; Mannan; FT-IR; DFT; Molecular modelling; Palm kernel...

Synthesis, spectroscopic (FT-IR, FT-Raman, NMR, UV-Visible), NLO, NBO, HOMO-LUMO, Fukui function and molecular docking study of (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide

Science.gov (United States)

Raja, M.; Raj Muhamed, R.; Muthu, S.; Suresh, M.

2017-08-01

The title compound, (E)-1-(5-bromo-2-hydroxybenzylidene)semicarbazide (15BHS) was synthesized and characterized by FT-IR, FT-Raman, UV, 1HNMR and 13CNMR spectral analysis. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and the Raman scattering activities were calculated by using density functional theory(DFT) B3LYP method with 6-311++G(d,p) basis set. The detailed interpretation of the vibrational spectra has been carried out by VEDA program. The calculated HOMO and LUMO energies show that charge transfer within the molecule. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital analysis (NBO). The first order hyperpolarizability, Molecular electrostatic potential (MEP) and Fukui functions were also performed. To study the biological activity of the investigation molecule, molecular docking was done to identify the hydrogen bond lengths and binding energy with different antifungal proteins. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the 15BHS at different temperatures have been calculated.

Process and system for isotope separation using the selective vibrational excitation of molecules

International Nuclear Information System (INIS)

Woodroffe, J.A.; Keck, J.C.

1976-01-01

This invention concerns the separation of isotopes by using the isotopically selective vibrational excitation and the vibration-translation reactions of the excited particles. UF 6 molecular mixed with a carrier gas, such as argon, are directed through a refrigerated chamber lighted by a laser radiation tuned to excite vibrationally the uranium hexafluoride molecules of a particular uranium isotope. The density of the carrier gas is preferably maintained above the density of the uranium hexafluoride to allow a greater collision probability of the vibrationally excited molecules with a carried molecule. In such a case, the vibrationally excited uranium hexafluoride will collide with a carrier gas molecule provoking the conversion of the excitation energy into a translation of the excited molecule, resulting in thermal energy or greater diffusibility than that of the other uranium hexafluoride molecules [fr

The discrimination of 72 nitrate, chlorate and perchlorate salts using IR and Raman spectroscopy

Science.gov (United States)

Zapata, Félix; García-Ruiz, Carmen

2018-01-01

Inorganic oxidizing energetic salts including nitrates, chlorates and perchlorates are widely used in the manufacture of not only licit pyrotechnic compositions, but also illicit homemade explosive mixtures. Their identification in forensic laboratories is usually accomplished by either capillary electrophoresis or ion chromatography, with the disadvantage of dissociating the salt into its ions. On the contrary, vibrational spectroscopy, including IR and Raman, enables the non-invasive identification of the salt, i.e. avoiding its dissociation. This study focuses on the discrimination of all nitrate, chlorate and perchlorate salts that are commercially available, using both Raman and IR spectroscopy, with the aim of testing whether every salt can be unequivocally identified. Besides the visual spectra comparison by assigning every band with the corresponding molecular vibrational mode, a statistical analysis based on Pearson correlation was performed to ensure an objective identification, either using Raman, IR or both. Positively, 25 salts (out of 72) were unequivocally identified using Raman, 30 salts when using IR and 44 when combining both techniques. Negatively, some salts were undistinguishable even using both techniques demonstrating there are some salts that provide very similar Raman and IR spectra.

Suppression of superconductivity in Nb by IrMn in IrMn/Nb bilayers

KAUST Repository

Wu, B. L.

2013-10-10

Effect of antiferromagnet on superconductivity has been investigated in IrMn/Nb bilayers. Significant suppression of both transition temperature (Tc) and lower critical field (Hc1) of Nb is found in IrMn/Nb bilayers as compared to a single layer Nb of same thickness; the suppression effect is even stronger than that of a ferromagnet in NiFe/Nb bilayers. The addition of an insulating MgO layer at the IrMn-Nb interface nearly restores Tc to that of the single layer Nb, but Hc1 still remains suppressed. These results suggest that, in addition to proximity effect and magnetic impurity scattering, magnetostatic interaction also plays a role in suppressing superconductivity of Nb in IrMn/Nb bilayers. In addition to reduced Tc and Hc1, the IrMn layer also induces broadening in the transition temperature of Nb, which can be accounted for by a finite distribution of stray field from IrMn.

Structural, spectroscopic (FT-IR, NMR, UV-visible), nonlinear optical (NLO), cytotoxic and molecular docking studies of 4-nitro-isonitrosoacetophenone (ninapH) by DFT method

Science.gov (United States)

Kucuk, Ilhan; Kaya, Yunus; Kaya, A. Asli

2017-07-01

(4-Nitro-phenyl)-oxo-acetaldehyde oxime (ninapH) is a type of oxime, which has a oxime and α-carbonyl groups. This molecule has been synthesized from literature procedure. The structural properties and conformational behaviors were examined using the density functional theory (DFT) with the B3LYP method combined with the 6-311++G(d,p) basis set. As a result of the conformational studies, the most stable conformer was determined, and then this molecule was optimized with the same basis set. Comprehensive theoretical and experimental structural studies on the molecule have been carried out by FT-IR, NMR and UV-vis spectrometry. The calculated HOMO and LUMO energies show that charge transfer within the molecule. The first order hyperpolarizability and molecular electrostatic potential (MEP) were also performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the ninapH have been calculated at different temperatures, 100-1000 K. In addition, the molecular docking studies have been performed with DNA and protein structures (downloaded from Protein Data Bank).

Probing wavenumbers of current-induced excitations in point-contact experiments

Directory of Open Access Journals (Sweden)

Z Wei

2010-06-01

Full Text Available Z Wei, M TsoiDepartment of Physics, Center for Nano and Molecular Science and Technology, and Texas Materials Institute, The University of Texas at Austin, Austin, TX, USAAbstract: We demonstrate how a mechanical point-contact technique can provide information on the wavenumber of spin waves excited by high-density electrical current in magnetic multilayers. By varying the size of point-contacts, we have been able to control the size of the excitation volume and therefore the wavelength of current-induced spin waves. This leads to a technique with in situ sensitivity to wavenumbers of current-induced excitations. Our detailed size-dependent measurements support the prediction that the excited wavelength is determined by the contact size.Keywords: spin transfer torque, giant magnetoresistance, spin waves, point contact

Optical and near-IR study of LMC HII region N11AB

International Nuclear Information System (INIS)

Lee, M.G.

1990-01-01

N11 (DEM 34), complex HII region located about 4 degrees from the center of the LMC bar, is a very interesting giant interstellar shell. It has a complicated structure and motion. It is located on the edge of an HI concentration. This is the progress report of the study of its two components, A and B at the optical and near-IR wavelengths to investigate stars, dust and ionized gas associated with them. N11A is a compact high-excitation blob and N11B is a bright HII region in this complex, which embeds OB association Lucke-Hodge 10

Excitation of atoms and molecules in collisions with highly charged ions

International Nuclear Information System (INIS)

Watson, R.L.

1992-01-01

This report discusses research of multicharged nitrogen, oxygen and carbon monoxide molecular ions produced with collision with multicharged argon ions. Properties like ionization, dissociation, and excitation are investigated

Rearrangements in ground and excited states

CERN Document Server

de Mayo, Paul

1980-01-01

Rearrangements in Ground and Excited States, Volume 2 covers essays on the theoretical approach of rearrangements; the rearrangements involving boron; and the molecular rearrangements of organosilicon compounds. The book also includes essays on the polytopal rearrangement at phosphorus; the rearrangement in coordination complexes; and the reversible thermal intramolecular rearrangements of metal carbonyls. Chemists and people involved in the study of rearrangements will find the book invaluable.

Adhesion of Photon-Driven Molecular Motors to Surfaces via 1,3-Dipolar Cycloadditions : Effect of Interfacial Interactions on Molecular Motion

NARCIS (Netherlands)

Carroll, Gregory T.; London, Gabor; Fernández Landaluce, Tatiana; Rudolf, Petra; Feringa, Ben L.

We report the attachment of altitudinal light-driven molecular motors to surfaces using 1,3-dipolar cycloaddition reactions. Molecular motors were designed containing azide or alkyne groups for attachment to alkyne- or azide-modified surfaces. Surface attachment was characterized by UV-vis, IR, XPS,

DFT, FT-IR, FT-Raman and vibrational studies of 3-methoxyphenyl boronic acid

Science.gov (United States)

Patil, N. R.; Hiremath, Sudhir M.; Hiremath, C. S.

2018-05-01

The aim of this work is to study the possible stable, geometrical molecular structure, experimental and theoretical FT-IR and FT-Raman spectroscopic methods of 3-Methoxyphenyl boronic acid (3MPBA). FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 40000-50 cm-1 respectively. The optimized geometric structure and vibrational wavenumbers of the title compound were searched by B3LYP hybrid density functional theory method with 6-311++G (d, p) basis set. The Selectedexperimentalbandswereassignedandcharacterizedonthebasisofthescaledtheoreticalwavenumbersby their potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. Finally, the predicted calculation results were applied to simulated FT-IR and FT-Raman spectra of the title compound, which show agreement with the observed spectra. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

Non-orthogonal configuration interaction for the calculation of multielectron excited states

Energy Technology Data Exchange (ETDEWEB)

Sundstrom, Eric J., E-mail: eric.jon.sundstrom@berkeley.edu; Head-Gordon, Martin [Department of Chemistry, University of California Berkeley, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

2014-03-21

We apply Non-orthogonal Configuration Interaction (NOCI) to molecular systems where multielectron excitations, in this case double excitations, play a substantial role: the linear polyenes and β-carotene. We demonstrate that NOCI when applied to systems with extended conjugation, provides a qualitatively correct wavefunction at a fraction of the cost of many other multireference treatments. We also present a new extension to this method allowing for purification of higher-order spin states by utilizing Generalized Hartree-Fock Slater determinants and the details for computing 〈S{sup 2}〉 for the ground and excited states.

Excitation-scanning hyperspectral imaging as a means to discriminate various tissues types

Science.gov (United States)

Deal, Joshua; Favreau, Peter F.; Lopez, Carmen; Lall, Malvika; Weber, David S.; Rich, Thomas C.; Leavesley, Silas J.

2017-02-01

Little is currently known about the fluorescence excitation spectra of disparate tissues and how these spectra change with pathological state. Current imaging diagnostic techniques have limited capacity to investigate fluorescence excitation spectral characteristics. This study utilized excitation-scanning hyperspectral imaging to perform a comprehensive assessment of fluorescence spectral signatures of various tissues. Immediately following tissue harvest, a custom inverted microscope (TE-2000, Nikon Instruments) with Xe arc lamp and thin film tunable filter array (VersaChrome, Semrock, Inc.) were used to acquire hyperspectral image data from each sample. Scans utilized excitation wavelengths from 340 nm to 550 nm in 5 nm increments. Hyperspectral images were analyzed with custom Matlab scripts including linear spectral unmixing (LSU), principal component analysis (PCA), and Gaussian mixture modeling (GMM). Spectra were examined for potential characteristic features such as consistent intensity peaks at specific wavelengths or intensity ratios among significant wavelengths. The resultant spectral features were conserved among tissues of similar molecular composition. Additionally, excitation spectra appear to be a mixture of pure endmembers with commonalities across tissues of varied molecular composition, potentially identifiable through GMM. These results suggest the presence of common autofluorescent molecules in most tissues and that excitationscanning hyperspectral imaging may serve as an approach for characterizing tissue composition as well as pathologic state. Future work will test the feasibility of excitation-scanning hyperspectral imaging as a contrast mode for discriminating normal and pathological tissues.

Using ATR-FT/IR to detect carbohydrate-related molecular structure features of carinata meal and their in situ residues of ruminal fermentation in comparison with canola meal

Science.gov (United States)

Xin, Hangshu; Yu, Peiqiang

2013-10-01

There is no information on the co-products from carinata bio-fuel and bio-oil processing (carinata meal) in molecular structural profiles mainly related to carbohydrate biopolymers in relation to ruminant nutrition. Molecular analyses with Fourier transform infrared spectroscopy (FT/IR) technique with attenuated total reflectance (ATR) and chemometrics enable to detect structural features on a molecular basis. The objectives of this study were to: (1) determine carbohydrate conformation spectral features in original carinata meal, co-products from bio-fuel/bio-oil processing; and (2) investigate differences in carbohydrate molecular composition and functional group spectral intensities after in situ ruminal fermentation at 0, 12, 24 and 48 h compared to canola meal as a reference. The molecular spectroscopic parameters of carbohydrate profiles detected were structural carbohydrates (STCHO, mainly associated with hemi-cellulosic and cellulosic compounds; region and baseline ca. 1483-1184 cm-1), cellulosic compounds (CELC, region and baseline ca. 1304-1184 cm-1), total carbohydrates (CHO, region and baseline ca. 1193-889 cm-1) as well as the spectral ratios calculated based on respective spectral intensity data. The results showed that the spectral profiles of carinata meal were significantly different from that of canola meal in CHO 2nd peak area (center at ca. 1091 cm-1, region: 1102-1083 cm-1) and functional group peak intensity ratios such as STCHO 1st peak (ca. 1415 cm-1) to 2nd peak (ca. 1374 cm-1) height ratio, CHO 1st peak (ca. 1149 cm-1) to 3rd peak (ca. 1032 cm-1) height ratio, CELC to total CHO area ratio and STCHO to CELC area ratio, indicating that carinata meal may not in full accord with canola meal in carbohydrate utilization and availability in ruminants. Carbohydrate conformation and spectral features were changed by significant interaction of meal type and incubation time and almost all the spectral parameters were significantly decreased (P

Hydrogen bonded supra-molecular framework in inorganic-organic hybrid compounds: Syntheses, structures, and photoluminescent properties

Science.gov (United States)

Yan, Li; Liu, Wei; Li, Chuanbi; Wang, Yifei; Ma, Li; Dong, Qinqin

2013-03-01

Two novel compounds constructed from aromatic acid and N-Heterocyclic ligands have been synthesized by hydrothermal reaction: [Cd(mip)(1,8-NDC)(H2O)]2 (1) [mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, 1,8-NDC = naphthalene-1,8-dicarboxylic acid] and Cd(mip)2(NTC)2 (2) [NTC = nicotinic acid]. Compounds 1 and 2 are characterized by elemental analysis, IR, single crystal X-ray diffraction and thermogravimetric analysis (TGA). Single-crystal X-ray investigation reveals that compounds 1-2 are 0 dimensional (0D) structures, and the existence of hydrogen bonds and π-π interactions lead the 0D to 2D novel framework. Hydrogen bonds and π-π interactions are powerful non-covalent intermolecular interactions for directing supra-molecular architectures. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. At room temperature, compound 1 exhibits emission at 449 nm upon excitation at 325 nm, and compound 2 shows a strong emission at 656 nm upon excitation at 350 nm. Fluorescent spectrum displays that compounds 1 and 2 are potential luminescent materials.

Molecular-beam scattering

International Nuclear Information System (INIS)

Vernon, M.F.

1983-07-01

The molecular-beam technique has been used in three different experimental arrangements to study a wide range of inter-atomic and molecular forces. Chapter 1 reports results of a low-energy (0.2 kcal/mole) elastic-scattering study of the He-Ar pair potential. The purpose of the study was to accurately characterize the shape of the potential in the well region, by scattering slow He atoms produced by expanding a mixture of He in N 2 from a cooled nozzle. Chapter 2 contains measurements of the vibrational predissociation spectra and product translational energy for clusters of water, benzene, and ammonia. The experiments show that most of the product energy remains in the internal molecular motions. Chapter 3 presents measurements of the reaction Na + HCl → NaCl + H at collision energies of 5.38 and 19.4 kcal/mole. This is the first study to resolve both scattering angle and velocity for the reaction of a short lived (16 nsec) electronic excited state. Descriptions are given of computer programs written to analyze molecular-beam expansions to extract information characterizing their velocity distributions, and to calculate accurate laboratory elastic-scattering differential cross sections accounting for the finite apparatus resolution. Experimental results which attempted to determine the efficiency of optically pumping the Li(2 2 P/sub 3/2/) and Na(3 2 P/sub 3/2/) excited states are given. A simple three-level model for predicting the steady-state fraction of atoms in the excited state is included

vuv fluorescence from selective high-order multiphoton excitation of N2

International Nuclear Information System (INIS)

Coffee, Ryan N.; Gibson, George N.

2004-01-01

Recent fluorescence studies suggest that ultrashort pulse laser excitation may be highly selective. Selective high-intensity laser excitation holds important consequences for the physics of multiphoton processes. To establish the extent of this selectivity, we performed a detailed comparative study of the vacuum ultraviolet fluorescence resulting from the interaction of N 2 and Ar with high-intensity infrared ultrashort laser pulses. Both N 2 and Ar reveal two classes of transitions, inner-valence ns ' l ' . From their pressure dependence, we associate each transition with either plasma or direct laser excitation. Furthermore, we qualitatively confirm such associations with the time dependence of the fluorescence signal. Remarkably, only N 2 presents evidence of direct laser excitation. This direct excitation produces ionic nitrogen fragments with inner-valence (2s) holes, two unidentified transitions, and one molecular transition, the N 2 + :X 2 Σ g + 2 Σ u + . We discuss these results in the light of a recently proposed model for multiphoton excitation

Porcine insulin receptor substrate 4 (IRS4) gene: cloning, polymorphism and association study

Czech Academy of Sciences Publication Activity Database

Masopust, Martin; Vykoukalová, Z.; Knoll, Aleš; Bartenschlager, H.; Mileham, A.; Deeb, N.; Rohrer, G. A.; Čepica, Stanislav

2010-01-01

Roč. 38, - (2010), 2611-2617 ISSN 0301-4851 R&D Projects: GA ČR GA523/07/0353; GA ČR GAP502/10/1216 Institutional research plan: CEZ:AV0Z50450515 Keywords : PCR cloning * Polymorphism * IRS4 Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 1.875, year: 2010

Sub-threshold excited Cl Kβ (K-V) x-ray fluorescence from CF3Cl molecule

International Nuclear Information System (INIS)

Perera, R.C.C.; Cowan, P.L.; Lindle, D.W.; LaVilla, R.E.

1987-10-01

With the availability of tunable synchrotron radiation sources, unoccupied molecular orbits (below vacuum level) can be selectively populated producing highly excited neutral molecules. X-ray fluorescence spectra from molecules were obtained with excitation below the ionization threshold and were observed to have significant intensity changes, absolute and relative energy position shifts and line width changes as compared to fluorescence spectra excited above the threshold. As an example, the Cl Kβ (K-V) emission spectra from CF 3 Cl vapor are presented. The energy shifts and intensity changes are explained in terms of perturbation effects due to the presence of an electron in an unoccupied molecular orbital. The narrow line widths obtained in the spectra excited below threshold are explained in terms of the ''effective'' hole production region in a core state limited by the broadening of the unoccupied level. The change in line widths as a function of below-threshold excitation energy is proposed as a novel technique to study the localized properties and reorganization effects of a hole in a core level. 10 refs., 4 figs., 1 tab

Using FT-IR Spectroscopy to Elucidate the Structures of Ablative Polymers

Science.gov (United States)

Fan, Wendy

2011-01-01

The composition and structure of an ablative polymer has a multifaceted influence on its thermal, mechanical and ablative properties. Understanding the molecular level information is critical to the optimization of material performance because it helps to establish correlations with the macroscopic properties of the material, the so-called structure-property relationship. Moreover, accurate information of molecular structures is also essential to predict the thermal decomposition pathways as well as to identify decomposition species that are fundamentally important to modeling work. In this presentation, I will describe the use of infrared transmission spectroscopy (FT-IR) as a convenient tool to aid the discovery and development of thermal protection system materials.

Ngc7538 Irs1 - A Highly Collimated Ionized Wind Source Powered By Accretion

Science.gov (United States)

Sandell, Goran H. L.; Wright, M.; Goss, W.; Corder, S.

2009-01-01

Recent images show that NGC7538 IRS1 is not a conventional Ultracompact or Hypercompact HII region, but is completely wind-excited (other broad recombination line hypercompact HII regions may be similar to IRS1). NGC 7538 IRS1 is a well studied young high-mass star (L 2 10^5 L_Sun).VLA images at 6 and 2 cm (Cambell 1984; ApJ, 282, L27) showed a compact bipolar core (lobe separation 0.2") with more extended faint lobes. Recombination line observations (Gaume et al. 1995, ApJ, 438, 776) show extremely wide line profiles indicating substantial mass motion of the ionized gas. We re-analyzed high angular resolution VLA archive data from 6 cm to 7 mm, and measured the flux from the compact core and the extended (1.5 - 2") bipolar lobes. We find that the compact core has a spectral index, alpha 0.6, which could be explained by an optically thick hypercompact core with a density gradient. However, the size of the core shrinks with increasing frequency; from 0.24" at 6 cm to 0.1" at 7 mm, consistent with that expected for a collimated jet (Reynolds 1986, ApJ, 304, 713). If we do a crude size correction so that we compare emission from the optically thick inner part of the jet for a set of 2 cm and 7 mm observations we get alpha 1.6, i.e. close to the optically thick value. BIMA and CARMA continuum observations at 3 mm show some dust excess, while. HCO+ J=1-0 observations combined with FCRAO single dish data show a clear inverse P Cygni profile towards IRS1. These observations confirm that IRS1 is heavily accreting with an accretion rate 2 10^-4 M_Sun/year, sufficient to quench the formation of an HII region.

An improved synthesis, spectroscopic (FT-IR, NMR) study and DFT computational analysis (IR, NMR, UV-Vis, MEP diagrams, NBO, NLO, FMO) of the 1,5-methanoazocino[4,3-b]indole core structure

Science.gov (United States)

Uludağ, Nesimi; Serdaroğlu, Goncagül

2018-03-01

This study examines the synthesis of azocino[4,3-b]indole structure, which constitutes the tetracyclic framework of uleine, dasycarpidoneand tubifolidineas well as ABDE substructure of the strychnosalkaloid family. It has been synthesized by Fischer indolization of 2 and through the cylization of 4 by 2,3-dichlor-5-6-dicyanobenzoquinone (DDQ). 1H and 1C NMR chemical shifts have been predicted with GIAO approach and the calculated chemical shifts show very good agreement with observed shifts. FT-IR spectroscopy is important for the analysis of functional groups of synthesized compounds and we also supported FT-IR vibrational analysis with computational IR analysis. The vibrational spectral analysis was performed at B3LYP level of the theory in both the gas and the water phases and it was compared with the observed IR values for the important functional groups. The DFT calculations have been conducted to determine the most stable structure of the 1,2,3,4,5,6,7-Hexahydro-1,5-methanoazocino [4,3-b] indole (5). The Frontier Molecular Orbital Analysis, quantum chemical parameters, physicochemical properties have been predicted by using the same theory of level in both gas phase and the water phase, at 631 + g** and 6311++g** basis sets. TD- DFT calculations have been performed to predict the UV- Vis spectral analysis for this synthesized molecule. The Natural Bond Orbital (NBO) analysis have been performed at B3LYP level of theory to elucidate the intra-molecular interactions such as electron delocalization and conjugative interactions. NLO calculations were conducted to obtain the electric dipole moment and polarizability of the title compound.

Mesoporous silica nanoparticle supported PdIr bimetal catalyst for selective hydrogenation, and the significant promotional effect of Ir

Energy Technology Data Exchange (ETDEWEB)

Yang, Hui; Huang, Chao; Yang, Fan [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); Yang, Xu [Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou (China); Du, Li [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou (China); Liao, Shijun, E-mail: chsjliao@scut.edu.cn [The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China); Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou (China)

2015-12-01

Graphical abstract: A mesoporous silica nanoparticle (MSN) supported bimetal catalyst, PdIr/MSN, was prepared by a facile impregnation and hydrogen reduction method. The strong promotional effect of Ir was observed and thoroughly investigated. At the optimal molar ratio of Ir to Pd (N{sub Ir}/N{sub Pd} = 0.1), the activity of PdIr{sub 0.1}/MSN was up to eight times and 28 times higher than that of monometallic Pd/MSN and Ir/MSN, respectively. The catalysts were characterized comprehensively by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen temperature programmed reduction, which revealed that the promotional effect of Ir may be due to the enhanced dispersion of active components on the MSN, and to the intensified Pd–Ir electronic interaction caused by the addition of Ir. - Highlights: • Mesoporous nanoparticles were synthesized and used as support for metal catalyst. • PdIr bimetallic catalyst exhibited significantly improved hydrogenation activity. • The strong promotion of Ir was recognized firstly and investigated intensively. • PdIr exhibits 18 times higher activity than Pd to the hydrogenation of nitrobenzene. - Abstract: A mesoporous silica nanoparticle (MSN) supported bimetal catalyst, PdIr/MSN, was prepared by a facile impregnation and hydrogen reduction method. The strong promotional effect of Ir was observed and thoroughly investigated. At the optimal molar ratio of Ir to Pd (N{sub Ir}/N{sub Pd} = 0.1), the activity of PdIr{sub 0.1}/MSN was up to eight times and 28 times higher than that of monometallic Pd/MSN and Ir/MSN, respectively. The catalysts were characterized comprehensively by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen temperature programmed reduction, which revealed that the promotional effect of Ir may be due to the enhanced dispersion of active components on the MSN, and to the intensified Pd–Ir electronic interaction

Studies on molecular structure, vibrational spectra and molecular docking analysis of 3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl 4-aminobenzoate

Science.gov (United States)

Suresh, D. M.; Amalanathan, M.; Hubert Joe, I.; Bena Jothy, V.; Diao, Yun-Peng

2014-09-01

The molecular structure, vibrational analysis and molecular docking analysis of the 3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl 4-aminobenzoate (MDDNAB) molecule have been carried out using FT-IR and FT-Raman spectroscopic techniques and DFT method. The equilibrium geometry, harmonic vibrational wave numbers, various bonding features have been computed using density functional method. The calculated molecular geometry has been compared with experimental data. The detailed interpretation of the vibrational spectra has been carried out by using VEDA program. The hyper-conjugative interactions and charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The simulated FT-IR and FT-Raman spectra satisfactorily coincide with the experimental spectra. The PES and charge analysis have been made. The molecular docking was done to identify the binding energy and the Hydrogen bonding with the cancer protein molecule.

BOOTES-IR: near IR follow-up GRB observations by a robotic system

International Nuclear Information System (INIS)

Castro-Tirado, A.J.; Postrigo, A. de Ugarte; Jelinek, M.

2005-01-01

BOOTES-IR is the extension of the BOOTES experiment, which operates in Southern Spain since 1998, to the near IR (NIR). The goal is to follow up the early stage of the gamma ray burst (GRB) afterglow emission in the NIR, alike BOOTES does already at optical wavelengths. The scientific case that drives the BOOTES-IR performance is the study of GRBs with the support of spacecraft like INTEGRAL, SWIFT and GLAST. Given that the afterglow emission in both, the NIR and the optical, in the instances immediately following a GRB, is extremely bright (reached V = 8.9 in one case), it should be possible to detect this prompt emission at NIR wavelengths too. The combined observations by BOOTES-IR and BOOTES-1 and BOOTES-2 will allow for real time identification of trustworthy candidates to have a high redshift (z > 5). It is expected that, few minutes after a GRB, the IR magnitudes be H ∼ 7-10, hence very high quality spectra can be obtained for objects as far as z = 10 by larger instruments

Development of Cytoplasmic Male Sterile IR24 and IR64 Using CW-CMS/Rf17 System.

Science.gov (United States)

Toriyama, Kinya; Kazama, Tomohiko

2016-12-01

A wild-abortive-type (WA) cytoplasmic male sterility (CMS) has been almost exclusively used for breeding three-line hybrid rice. Many indica cultivars are known to carry restorer genes for WA-CMS lines and cannot be used as maintainer lines. Especially elite indica cultivars IR24 and IR64 are known to be restorer lines for WA-CMS lines, and are used as male parents for hybrid seed production. If we develop CMS IR24 and CMS IR64, the combination of F1 pairs in hybrid rice breeding programs will be greatly broadened. For production of CMS lines and restorer lines of IR24 and IR64, we employed Chinese wild rice (CW)-type CMS/Restorer of fertility 17 (Rf17) system, in which fertility is restored by a single nuclear gene, Rf17. Successive backcrossing and marker-assisted selection of Rf17 succeeded to produce completely male sterile CMS lines and fully restored restorer lines of IR24 and IR64. CW-cytoplasm did not affect agronomic characteristics. Since IR64 is one of the most popular mega-varieties and used for breeding of many modern varieties, the CW-CMS line of IR64 will be useful for hybrid rice breeding.

Capture, excitation and ionization in H++He+(1s) collisions

International Nuclear Information System (INIS)

Harel, C.; Mendez, L.; Riera, A.

1995-01-01

Capture, excitation and ionization cross sections have been calculated for the H + +He + (1s) reaction up to v=3 a.u. in a sole theoretical formalism. An extension to the intermediate energy range of the molecular method including distorded molecular orbitals to discretize the continuum is used. Our results for the three inelastic processes are in very good agreement with both experimental and previous theoretical data. (orig.)

The TApIR experiment. IR absorption spectra of liquid hydrogen isotopologues

International Nuclear Information System (INIS)

Groessle, Robin

2015-01-01

The scope of the thesis is the infrared absorption spectroscopy of liquid hydrogen isotopologues with the tritium absorption infrared spectroscopy (TApIR) experiment at the tritium laboratory Karlsruhe (TLK). The calibration process from the sample preparation to the reference measurements are described. A further issue is the classical evaluation of FTIR absorption spectra and the extension using the rolling circle filter (RCF) including the effects on statistical and systematical errors. The impact of thermal and nuclear spin temperature on the IR absorption spectra is discussed. An empirical based modeling for the IR absorption spectra of liquid hydrogen isotopologues is performed.

Charge-Transfer Dynamics in the Lowest Excited State of a Pentacene–Fullerene Complex: Implications for Organic Solar Cells

KAUST Repository

Joseph, Saju

2017-10-02

We characterize the dynamic nature of the lowest excited state in a pentacene/C60 complex on the femtosecond time scale, via a combination of ab initio molecular dynamics and time-dependent density functional theory. We analyze the correlations between the molecular vibrations of the complex and the oscillations in the electron-transfer character of its lowest excited state, which point to vibration-induced coherences between the (pentacene-based) local-excitation (LE) state and the complex charge-transfer (CT) state. We discuss the implications of our results on this model system for the exciton-dissociation process in organic solar cells.

Upper limits to the detection of ammonia from protoplanetary disks around HL Tauri and L1551-IRS 5

Science.gov (United States)

Gomez, Jose F.; Torrelles, Jose M.; Ho, Paul T. P.; Rodriguez, Luis F.; Canto, Jorge

1993-01-01

We present NH3(1, 1) and (2, 2) observations of the young stellar sources HL Tau and L1551-IRS 5 using the VLA in its B-configuration, which provides an angular resolution of about 0.4 arcsec (about 50 AU at 140 pc) at 1.3 cm wavelength. Our goal was to detect and resolve circumstellar molecular disks with radius of the order of 100 AU around these two sources. No ammonia emission was detected toward either of them. The 3-sigma levels were 2.7 mJy/beam and 3.9 mJy/beam for HL Tau and L1551-IRS 5, respectively, with a velocity resolution of about 5 km/s. With this nondetection, we estimate upper limits to the mass of the proposed protoplanetary molecular disks (within a radius of 10 AU from the central stars) on the order of 0.02/(X(NH3)/10 exp -8) solar mass for HL Tau and 0.1/(X(NH3)/10 exp -8) solar mass for L1551-IRS 5.

Unraveling the Mechanism of a Reversible Photoactivated Molecular Proton Crane

NARCIS (Netherlands)

van der Loop, T.H.; Ruesink, F.; Amirjalayer, S.; Sanders, H. J.; Buma, W.J.; Woutersen, S.

2014-01-01

Structural dynamics of the photoactivated mol. proton crane 7-​hydroxy-​8-​(morpholinomethyl)​quinoline has been studied using femtosecond UV-​pump IR-​probe spectroscopy. Upon electronic excitation, a proton is transferred from the hydroxy to the amine group located on the rotatable morpholino side

TDDFT study on intramolecular hydrogen bond of photoexcited methyl salicylate.

Science.gov (United States)

Qu, Peng; Tian, Dongxu

2014-01-01

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

Atomic and molecular data for radiotherapy

International Nuclear Information System (INIS)

1989-05-01

An Advisory Group Meeting devoted solely to review the atomic and molecular data needed for radiotherapy was held in Vienna from 13 to 16 June 1988. The following items as related to the atoms and molecules of human tissues were reviewed: Cross sections differential in energy loss for electrons and other charged particles. Secondary electron spectra, or differential ionization cross sections. Total cross sections for ionization and excitation. Subexcitation electrons. Cross sections for charged-particle collisions in condensed matter. Stopping power for low-energy electrons and ions. Initial yields of atomic and molecular ions and their excited states and electron degradation spectra. Rapid conversion of these initial ions and their excited states through thermal collisions with other atoms and molecules. Track-structure quantities. Other relevant data. Refs, figs and tabs

Identification of Serine Conformers by Matrix-Isolation IR Spectroscopy Aided by Near-Infrared Laser-Induced Conformational Change, 2D Correlation Analysis, and Quantum Mechanical Anharmonic Computations.

Science.gov (United States)

Najbauer, Eszter E; Bazsó, Gábor; Apóstolo, Rui; Fausto, Rui; Biczysko, Malgorzata; Barone, Vincenzo; Tarczay, György

2015-08-20

The conformers of α-serine were investigated by matrix-isolation IR spectroscopy combined with NIR laser irradiation. This method, aided by 2D correlation analysis, enabled unambiguously grouping the spectral lines to individual conformers. On the basis of comparison of at least nine experimentally observed vibrational transitions of each conformer with empirically scaled (SQM) and anharmonic (GVPT2) computed IR spectra, six conformers were identified. In addition, the presence of at least one more conformer in Ar matrix was proved, and a short-lived conformer with a half-life of (3.7 ± 0.5) × 10(3) s in N2 matrix was generated by NIR irradiation. The analysis of the NIR laser-induced conversions revealed that the excitation of the stretching overtone of both the side chain and the carboxylic OH groups can effectively promote conformational changes, but remarkably different paths were observed for the two kinds of excitations.

Analytic energy gradient of excited electronic state within TDDFT/MMpol framework: Benchmark tests and parallel implementation.

Science.gov (United States)

Zeng, Qiao; Liang, WanZhen

2015-10-07

The time-dependent density functional theory (TDDFT) has become the most popular method to calculate the electronic excitation energies, describe the excited-state properties, and perform the excited-state geometric optimization of medium and large-size molecules due to the implementation of analytic excited-state energy gradient and Hessian in many electronic structure software packages. To describe the molecules in condensed phase, one usually adopts the computationally efficient hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) models. Here, we extend our previous work on the energy gradient of TDDFT/MM excited state to account for the mutual polarization effects between QM and MM regions, which is believed to hold a crucial position in the potential energy surface of molecular systems when the photoexcitation-induced charge rearrangement in the QM region is drastic. The implementation of a simple polarizable TDDFT/MM (TDDFT/MMpol) model in Q-Chem/CHARMM interface with both the linear response and the state-specific features has been realized. Several benchmark tests and preliminary applications are exhibited to confirm our implementation and assess the effects of different treatment of environmental polarization on the excited-state properties, and the efficiency of parallel implementation is demonstrated as well.

Advances in molecular vibrations and collision dynamics molecular clusters

CERN Document Server

Bacic, Zatko

1998-01-01

This volume focuses on molecular clusters, bound by van der Waals interactions and hydrogen bonds. Twelve chapters review a wide range of recent theoretical and experimental advances in the areas of cluster vibrations, spectroscopy, and reaction dynamics. The authors are leading experts, who have made significant contributions to these topics.The first chapter describes exciting results and new insights in the solvent effects on the short-time photo fragmentation dynamics of small molecules, obtained by combining heteroclusters with femtosecond laser excitation. The second is on theoretical work on effects of single solvent (argon) atom on the photodissociation dynamics of the solute H2O molecule. The next two chapters cover experimental and theoretical aspects of the energetics and vibrations of small clusters. Chapter 5 describes diffusion quantum Monte Carlo calculations and non additive three-body potential terms in molecular clusters. The next six chapters deal with hydrogen-bonded clusters, refle...

Identification of the fragment of the 1-methylpyrene cation by mid-IR spectroscopy

Science.gov (United States)

Jusko, Pavol; Simon, Aude; Wenzel, Gabi; Brünken, Sandra; Schlemmer, Stephan; Joblin, Christine

2018-04-01

The fragment of the 1-methylpyrene cation, 17C 11H+, is expected to exist in two isomeric forms, 1-pyrenemethylium PyrCH2+ and the tropylium containing species PyrC7+. We measured the infrared (IR) action spectrum of cold 17C 11H+ tagged with Ne using a cryogenic ion trap instrument coupled to the FELIX laser. Comparison of the experimental data with density functional theory calculations allows us to identify the PyrCH2+ isomer in our experiments. The IR Multi-Photon Dissociation spectrum was also recorded following the C2H2 loss channel. Its analysis suggests combined effects of anharmonicity and isomerisation while heating the trapped ions, as shown by molecular dynamics simulations.

The molecular environment of the pillar-like features in the H II region G46.5-0.2

Science.gov (United States)

Paron, S.; Celis Peña, M.; Ortega, M. E.; Fariña, C.; Petriella, A.; Rubio, M.; Ashley, R. P.

2017-10-01

At the interface of H II regions and molecular gas, peculiar structures appear, some of them with pillar-like shapes. Understanding their origin is important for characterizing triggered star formation and the impact of massive stars on the interstellar medium. In order to study the molecular environment and influence of radiation on two pillar-like features related to the H II region G46.5-0.2, we performed molecular line observations with the Atacama Submillimeter Telescope Experiment and spectroscopic optical observations with the Isaac Newton Telescope. From the optical observations, we identified the star that is exciting the H II region as spectral type O4-6. The molecular data allowed us to study the structure of the pillars and an HCO+ cloud lying between them. In this HCO+ cloud, which has no well-defined 12CO counterpart, we found direct evidence of star formation: two molecular outflows and two associated near-IR nebulosities. The outflow axis orientation is perpendicular to the direction of the radiation flow from the H II region. Several Class I sources are also embedded in this HCO+ cloud, showing that it is usual that young stellar objects (YSOs) form large associations occupying a cavity bounded by pillars. On the other hand, it was confirmed that the radiation-driven implosion (RDI) process is not occurring in one of the pillar tips.

Quadrupole magnets for IR-FEL at RRCAT

International Nuclear Information System (INIS)

Ruwali, Kailash; Singh, Kushraj; Mishra, Anil Kumar; Biswas, Bhaskar

2013-01-01

The IR-FEL project at RRCAT needs quadrupole magnets for focusing 15 to 35 MeV electron beam through a dog-leg type beam line. This bend needs tighter relative tolerances on the central quadrupole triplet . The magnetic design, fabrication and magnetic characterization of five quadrupole magnets were carried out. The poles are detachable and wider than the coils. This significantly improves the good field region of the magnet. The magnet cross-section was optimized using 2D POISON code and entry-exit tapers were optimized using 3D code TOSCA.. The aperture radius of the magnet is 30 mm and the total core length is 180 mm. The integrated gradient of magnet is 0.51 T. The magnetic measurements were carried out using Danfysik make rotating coil bench model 690. Integrated gradient and multipoles present in the magnet aperture were measured at various excitation levels. The details of magnetic development and the magnetic measurements are discussed in this paper. (author)

Behavior of Excited Argon Atoms in Inductively Driven Plasmas

International Nuclear Information System (INIS)

HEBNER, GREGORY A.; MILLER, PAUL A.

1999-01-01

Laser induced fluorescence has been used to measure the spatial distribution of the two lowest energy argon excited states, 1s 5 and 1s 4 , in inductively driven plasmas containing argon, chlorine and boron trichloride. The behavior of the two energy levels with plasma conditions was significantly different, probably because the 1s 5 level is metastable and the 1s 4 level is radiatively coupled to the ground state but is radiation trapped. The argon data is compared with a global model to identify the relative importance of processes such as electron collisional mixing and radiation trapping. The trends in the data suggest that both processes play a major role in determining the excited state density. At lower rfpower and pressure, excited state spatial distributions in pure argon were peaked in the center of the discharge, with an approximately Gaussian profile. However, for the highest rfpowers and pressures investigated, the spatial distributions tended to flatten in the center of the discharge while the density at the edge of the discharge was unaffected. The spatially resolved excited state density measurements were combined with previous line integrated measurements in the same discharge geometry to derive spatially resolved, absolute densities of the 1s 5 and 1s 4 argon excited states and gas temperature spatial distributions. Fluorescence lifetime was a strong fi.mction of the rf power, pressure, argon fraction and spatial location. Increasing the power or pressure resulted in a factor of two decrease in the fluorescence lifetime while adding Cl 2 or BCl 3 increased the fluorescence lifetime. Excited state quenching rates are derived from the data. When Cl 2 or BCl 3 was added to the plasma, the maximum argon metastable density depended on the gas and ratio. When chlorine was added to the argon plasma, the spatial density profiles were independent of chlorine fraction. While it is energetically possible for argon excited states to dissociate some of the

Signal-to-noise ratio of FT-IR CO gas spectra

DEFF Research Database (Denmark)

Bak, J.; Clausen, Sønnik

1999-01-01

in emission and transmission spectrometry, an investigation of the SNR in CO gas spectra as a function of spectral resolution has been carried out. We present a method to (1) determine experimentally the SNR at constant throughput, (2) determine the SNR on the basis of measured noise levels and Hitran......The minimum amount of a gaseous compound which can be detected and quantified with Fourier transform infrared (FT-IR) spectrometers depends on the signal-to-noise ratio (SNR) of the measured gas spectra. In order to use low-resolution FT-IR spectrometers to measure combustion gases like CO and CO2...... simulated signals, and (3) determine the SNR of CO from high to low spectral resolutions related to the molecular linewidth and vibrational-rotational lines spacing. In addition, SNR values representing different spectral resolutions but scaled to equal measurement times were compared. It was found...

Cine: Line excitation by infrared fluorescence in cometary atmospheres

Science.gov (United States)

de Val-Borro, Miguel; Cordiner, Martin A.; Milam, Stefanie N.; Charnley, Steven B.

2017-03-01

CINE is a Python module for calculating infrared pumping efficiencies that can be applied to the most common molecules found in cometary comae such as water, hydrogen cyanide or methanol. Excitation by solar radiation of vibrational bands followed by radiative decay to the ground vibrational state is one of the main mechanisms for molecular excitation in comets. This code calculates the effective pumping rates for rotational levels in the ground vibrational state scaled by the heliocentric distance of the comet. Line transitions are queried from the latest version of the HITRAN spectroscopic repository using the astroquery affiliated package of astropy. Molecular data are obtained from the LAMDA database. These coefficients are useful for modeling rotational emission lines observed in cometary spectra at sub-millimeter wavelengths. Combined with computational methods to solve the radiative transfer equations based, e.g., on the Monte Carlo algorithm, this model can retrieve production rates and rotational temperatures from the observed emission spectrum.

Selective excitation, relaxation, and energy channeling in molecular systems

International Nuclear Information System (INIS)

Rhodes, W.C.

1993-08-01

Research involves theoretical studies of response, relaxation, and correlated motion in time-dependent behavior of large molecular systems ranging from polyatomic molecules to protein molecules in their natural environment. Underlying theme is subsystem modulation dynamics. Main idea is that quantum mechanical correlations between components of a system develop with time, playing a major role in determining the balance between coherent and dissipative forces. Central theme is interplay of coherence and dissipation in determining the nature of dynamic structuring and energy flow in molecular transformation mechanisms. Subsystem equations of motion are being developed to show how nonlinear, dissipative dynamics of a particular subsystem arise from correlated interactions with the rest of the system (substituent groups, solvent, lattice modes, etc.); one consequence is resonance structures and networks. Quantum dynamics and thermodynamics are being applied to understand control and energy transfer mechanisms in biological functions of protein molecules; these mechanisms are both global and local. Besides the above theory, the research deals with phenomenological aspects of molecular systems

Conformation of the azo bond and its influence on the molecular and crystal structures, IR and Raman spectra, and electron properties of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine - Quantum chemical DFT calculations

Science.gov (United States)

Michalski, J.; Bryndal, I.; Lorenc, J.; Hermanowicz, K.; Janczak, J.; Hanuza, J.

2018-02-01

The crystal and molecular structures of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine have been determined by X-ray diffraction and quantum chemical DFT calculations. The crystal is monoclinic, space group Cc (No. 9) with Z = 4 with the unit cell parameters: a = 12.083(7), b = 12.881(6), c = 8.134(3) Å and β = 97.09(5)°. The azo-bridge appears in the trans conformation in which C2-N2-N2‧-C1‧ torsion angle takes a value - 178.6(3)°, whereas the dihedral angle between the planes of the phenyl and pyridine rings is 3.5(2)°. The IR and Raman spectra measured in the temperature range 80-350 K and quantum chemical calculations with the use of B3LYP/6-311G(2d,2p) approach confirmed the trans configuration of the azo-bridge as the most stable energetically and allowed determination of the energy other virtual structures. The observed effects were used in the discussion of vibrational dynamics of the studied compound. The energy gap between cis and trans conformers equals to 1.054 eV (0.03873 Hartree). The electron absorption and emission spectra have been measured and analyzed on the basis of DFT calculations. The life time of the excited state is 12 μs and the Stokes shift is close to 5470 cm- 1.

Inhibition of PTP1B Restores IRS1-Mediated Hepatic Insulin Signaling in IRS2-Deficient Mice

Science.gov (United States)

González-Rodríguez, Águeda; Gutierrez, Jose A. Mas; Sanz-González, Silvia; Ros, Manuel; Burks, Deborah J.; Valverde, Ángela M.

2010-01-01

OBJECTIVE Mice with complete deletion of insulin receptor substrate 2 (IRS2) develop hyperglycemia, impaired hepatic insulin signaling, and elevated gluconeogenesis, whereas mice deficient for protein tyrosine phosphatase (PTP)1B display an opposing hepatic phenotype characterized by increased sensitivity to insulin. To define the relationship between these two signaling pathways in the regulation of liver metabolism, we used genetic and pharmacological approaches to study the effects of inhibiting PTP1B on hepatic insulin signaling and expression of gluconeogenic enzymes in IRS2−/− mice. RESEARCH DESIGN AND METHODS We analyzed glucose homeostasis and insulin signaling in liver and isolated hepatocytes from IRS2−/− and IRS2−/−/PTP1B−/− mice. Additionally, hepatic insulin signaling was assessed in control and IRS2−/− mice treated with resveratrol, an antioxidant present in red wine. RESULTS In livers of hyperglycemic IRS2−/− mice, the expression levels of PTP1B and its association with the insulin receptor (IR) were increased. The absence of PTP1B in the double-mutant mice restored hepatic IRS1-mediated phosphatidylinositol (PI) 3-kinase/Akt/Foxo1 signaling. Moreover, resveratrol treatment of hyperglycemic IRS2−/− mice decreased hepatic PTP1B mRNA and inhibited PTP1B activity, thereby restoring IRS1-mediated PI 3-kinase/Akt/Foxo1 signaling and peripheral insulin sensitivity. CONCLUSIONS By regulating the phosphorylation state of IR, PTB1B determines sensitivity to insulin in liver and exerts a unique role in the interplay between IRS1 and IRS2 in the modulation of hepatic insulin action. PMID:20028942

Excitation and characterization of image potential state electrons on quasi-free-standing graphene

Science.gov (United States)

Lin, Yi; Li, Yunzhe; Sadowski, Jerzy T.; Jin, Wencan; Dadap, Jerry I.; Hybertsen, Mark S.; Osgood, Richard M.

2018-04-01

We investigate the band structure of image potential states in quasi-free-standing graphene (QFG) monolayer islands using angle-resolved two-photon-photoemission spectroscopy. Direct probing by low-energy electron diffraction shows that QFG is formed following oxygen intercalation into the graphene-Ir(111) interface. Despite the apparent decoupling of the monolayer graphene from the Ir substrate, we find that the binding energy of the n =1 image potential state on these QFG islands increases by 0.17 eV, as compared to the original Gr/Ir(111) interface. We use calculations based on density-functional theory to construct an empirical, one-dimensional potential that quantitatively reproduces the image potential state binding energy and links the changes in the interface structure to the shift in energy. Specifically, two factors contribute comparably to this energy shift: a deeper potential well arising from the presence of intercalated oxygen adatoms and a wider potential well associated with the increase in the graphene-Ir distance. While image potential states have not been observed previously on QFG by photoemission, our paper now demonstrates that they may be strongly excited in a well-defined QFG system produced by oxygen intercalation. This opens an opportunity for studying the surface electron dynamics in QFG systems, beyond those found in typical nonintercalated graphene-on-substrate systems.

Validation of the thermal code of RadTherm-IR, IR-Workbench, and F-TOM

Science.gov (United States)

Schwenger, Frédéric; Grossmann, Peter; Malaplate, Alain

2009-05-01

System assessment by image simulation requires synthetic scenarios that can be viewed by the device to be simulated. In addition to physical modeling of the camera, a reliable modeling of scene elements is necessary. Software products for modeling of target data in the IR should be capable of (i) predicting surface temperatures of scene elements over a long period of time and (ii) computing sensor views of the scenario. For such applications, FGAN-FOM acquired the software products RadTherm-IR (ThermoAnalytics Inc., Calumet, USA; IR-Workbench (OKTAL-SE, Toulouse, France). Inspection of the accuracy of simulation results by validation is necessary before using these products for applications. In the first step of validation, the performance of both "thermal solvers" was determined through comparison of the computed diurnal surface temperatures of a simple object with the corresponding values from measurements. CUBI is a rather simple geometric object with well known material parameters which makes it suitable for testing and validating object models in IR. It was used in this study as a test body. Comparison of calculated and measured surface temperature values will be presented, together with the results from the FGAN-FOM thermal object code F-TOM. In the second validation step, radiances of the simulated sensor views computed by RadTherm-IR and IR-Workbench will be compared with radiances retrieved from the recorded sensor images taken by the sensor that was simulated. Strengths and weaknesses of the models RadTherm-IR, IR-Workbench and F-TOM will be discussed.

Lifetime in 181Ir and 187Au: enhanced deformation of the πi 13/2 intruder orbital

International Nuclear Information System (INIS)

Walpe, J.C.; Garg, U.; Naguleswaran, S.; Ren, Q.W.

1995-01-01

Lifetimes have been measured in the πh 9/2 (yrast) and πi 13/2 (excited) bands in the nuclei 181 Ir and 187 Au using the Recoil Distance Method (RDM). The results clearly indicate that the πi 13/2 band exhibits an increased deformation over the πh 9/2 band, in keeping with the premise that the delayed crossing in this band is due to enhanced quadrupole deformation. (author). 3 refs, 1 fig, 2 tab

Excited TBA equations I: Massive tricritical Ising model

International Nuclear Information System (INIS)

Pearce, Paul A.; Chim, Leung; Ahn, Changrim

2001-01-01

We consider the massive tricritical Ising model M(4,5) perturbed by the thermal operator phi (cursive,open) Greek 1,3 in a cylindrical geometry and apply integrable boundary conditions, labelled by the Kac labels (r,s), that are natural off-critical perturbations of known conformal boundary conditions. We derive massive thermodynamic Bethe ansatz (TBA) equations for all excitations by solving, in the continuum scaling limit, the TBA functional equation satisfied by the double-row transfer matrices of the A 4 lattice model of Andrews, Baxter and Forrester (ABF) in Regime III. The complete classification of excitations, in terms of (m,n) systems, is precisely the same as at the conformal tricritical point. Our methods also apply on a torus but we first consider (r,s) boundaries on the cylinder because the classification of states is simply related to fermionic representations of single Virasoro characters χ r,s (q). We study the TBA equations analytically and numerically to determine the conformal UV and free particle IR spectra and the connecting massive flows. The TBA equations in Regime IV and massless RG flows are studied in Part II

Near-infrared H2 emission from Herbig-Haro objects. I. A survey of low excitation objects

International Nuclear Information System (INIS)

Schwartz, R.D.; Cohen, M.; Williams, P.M.

1987-01-01

A survey for H 2 1-0 S(1) emission in 16 Herbig-Haro (HH) objects and three exciting stars for HH objects is reported. Eleven HH objects which show low-excitation optical spectra exhibit H 2 emission. One object (HH 43) is more than twice as bright as any previously reported HH object. In addition, spectra in the range 1.6-2.55 microns are reported for HH 43 and HH 120, and a 2.0-2.55 micron spectrum is presented for HH 26. The spectra yield estimates of the H 2 density and temperature ranges in these objects. The role of ultraviolet H 2 emission-line fluorescence in HH 43 with respect to cascading among excited vibrational states of the ground electronic state is discussed. Models which may account for the combined ultraviolet, optical, and near-IR spectra of HHs are briefly analyzed. 35 references

Hydrogenation of ethene catalyzed by Ir atom deposited on γ-Al2O3(001) surface: From ab initio calculations

International Nuclear Information System (INIS)

Chen, Yongchang; Sun, Zhaolin; Song, Lijuan; Li, Qiang; Xu, Ming

2012-01-01

Ethene hydrogenation reaction, catalyzed by an iridium atom adsorbed on γ-Al 2 O 3 (001) surface, is studied via ab initio calculations based on density functional theory (DFT). The catalyzed reaction process and activation energy are compared with the counterparts of a reaction occurs in vacuum condition. It is found that the activation energy barrier is substantially lowered by the adsorbed Ir atom on the γ-Al 2 O 3 (001). The catalyzed reaction is modeled in two steps: (1) Hydrogen molecular dissolution and then bonded with C 2 H 4 molecular. (2) Desorption of the C 2 H 6 molecular from the surface. -- Highlights: ► The ethene hydrogenation reaction is simulated with nudged elastic band methods. ► The catalytic effect of the Ir atom on γ-Al 2 O 3 (001) surface is modeled. ► Details of the catalytic reaction are exhibited.

STATYBINIŲ MEDŽIAGŲ KONKURENCINGUMAS IR TENDENCIJOS

OpenAIRE

Kontrimas, Robertas

2010-01-01

Darbe analizuojamas statybinių medžiagų konkurencingumas, nustatyti statybinių medžiagų konkurencingumą įtakojantys veiksniai ir pateikti pasiūlymai rinkos gerinimui. Pasitvirtino hipotezė, kad statybinių medžiagų paklausą ir kainas įtakoja klientų poreikiai ir jų finansinės galimybės, tačiau pasaulinės krizės įtaka yra labai ženkli,. Atlikta darbuotojų ir pirkėjų apklausa padėjo nustatyti, kokios statybinės medžiagos dažniausiai yra perkamos, kaip klientai ir darbuotojai vertina įmonę ir jos...

Restricted second random phase approximations and Tamm-Dancoff approximations for electronic excitation energy calculations

International Nuclear Information System (INIS)

Peng, Degao; Yang, Yang; Zhang, Peng; Yang, Weitao

2014-01-01

In this article, we develop systematically second random phase approximations (RPA) and Tamm-Dancoff approximations (TDA) of particle-hole and particle-particle channels for calculating molecular excitation energies. The second particle-hole RPA/TDA can capture double excitations missed by the particle-hole RPA/TDA and time-dependent density-functional theory (TDDFT), while the second particle-particle RPA/TDA recovers non-highest-occupied-molecular-orbital excitations missed by the particle-particle RPA/TDA. With proper orbital restrictions, these restricted second RPAs and TDAs have a formal scaling of only O(N 4 ). The restricted versions of second RPAs and TDAs are tested with various small molecules to show some positive results. Data suggest that the restricted second particle-hole TDA (r2ph-TDA) has the best overall performance with a correlation coefficient similar to TDDFT, but with a larger negative bias. The negative bias of the r2ph-TDA may be induced by the unaccounted ground state correlation energy to be investigated further. Overall, the r2ph-TDA is recommended to study systems with both single and some low-lying double excitations with a moderate accuracy. Some expressions on excited state property evaluations, such as 〈S ^2 〉 are also developed and tested

Restricted second random phase approximations and Tamm-Dancoff approximations for electronic excitation energy calculations

Energy Technology Data Exchange (ETDEWEB)

Peng, Degao; Yang, Yang; Zhang, Peng [Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States); Yang, Weitao, E-mail: weitao.yang@duke.edu [Department of Chemistry and Department of Physics, Duke University, Durham, North Carolina 27708 (United States)

2014-12-07

In this article, we develop systematically second random phase approximations (RPA) and Tamm-Dancoff approximations (TDA) of particle-hole and particle-particle channels for calculating molecular excitation energies. The second particle-hole RPA/TDA can capture double excitations missed by the particle-hole RPA/TDA and time-dependent density-functional theory (TDDFT), while the second particle-particle RPA/TDA recovers non-highest-occupied-molecular-orbital excitations missed by the particle-particle RPA/TDA. With proper orbital restrictions, these restricted second RPAs and TDAs have a formal scaling of only O(N{sup 4}). The restricted versions of second RPAs and TDAs are tested with various small molecules to show some positive results. Data suggest that the restricted second particle-hole TDA (r2ph-TDA) has the best overall performance with a correlation coefficient similar to TDDFT, but with a larger negative bias. The negative bias of the r2ph-TDA may be induced by the unaccounted ground state correlation energy to be investigated further. Overall, the r2ph-TDA is recommended to study systems with both single and some low-lying double excitations with a moderate accuracy. Some expressions on excited state property evaluations, such as 〈S{sup ^2}〉 are also developed and tested.

Self-Consistent Optimization of Excited States within Density-Functional Tight-Binding.

Science.gov (United States)

Kowalczyk, Tim; Le, Khoa; Irle, Stephan

2016-01-12

We present an implementation of energies and gradients for the ΔDFTB method, an analogue of Δ-self-consistent-field density functional theory (ΔSCF) within density-functional tight-binding, for the lowest singlet excited state of closed-shell molecules. Benchmarks of ΔDFTB excitation energies, optimized geometries, Stokes shifts, and vibrational frequencies reveal that ΔDFTB provides a qualitatively correct description of changes in molecular geometries and vibrational frequencies due to excited-state relaxation. The accuracy of ΔDFTB Stokes shifts is comparable to that of ΔSCF-DFT, and ΔDFTB performs similarly to ΔSCF with the PBE functional for vertical excitation energies of larger chromophores where the need for efficient excited-state methods is most urgent. We provide some justification for the use of an excited-state reference density in the DFTB expansion of the electronic energy and demonstrate that ΔDFTB preserves many of the properties of its parent ΔSCF approach. This implementation fills an important gap in the extended framework of DFTB, where access to excited states has been limited to the time-dependent linear-response approach, and affords access to rapid exploration of a valuable class of excited-state potential energy surfaces.

Initial vibrational and rotational yields from subexcitation electrons in molecular hydrogen

International Nuclear Information System (INIS)

Douthat, D.A.

1987-01-01

As the energy of a single source electron injected into a molecular gas is degraded through collisions, initial products include secondary electrons, ions, and excited molecules. Electrons with kinetic energies less than the minimum required for excitation of the lowest electronic state are given the designation subexcitation electrons. These electrons are still capable of exciting vibrational and rotational states of molecular gases. In this calculation, the initial numbers of vibrational and rotational excitations (yields) produced as the subexcitation electrons undergo further energy degradation are determined for molecular hydrogen. The calculation requires a complete set of cross section data for numerical solution of the Boltzmann equation. The initial energy distribution of electrons is taken to be the subexcitation distribution which was determined previously. The initial yields are tabulated for gas temperatures from 50 K to 1500 K for a source electron with initial energy 10 keV. 26 references

Discrimination of Chinese Sauce liquor using FT-IR and two-dimensional correlation IR spectroscopy

Science.gov (United States)

Sun, Su-Qin; Li, Chang-Wen; Wei, Ji-Ping; Zhou, Qun; Noda, Isao

2006-11-01

We applied the three-step IR macro-fingerprint identification method to obtain the IR characteristic fingerprints of so-called Chinese Sauce liquor (Moutai liquor and Kinsly liquor) and a counterfeit Moutai. These fingerprints can be used for the identification and discrimination of similar liquor products. The comparison of their conventional IR spectra, as the first step of identification, shows that the primary difference in Sauce liquor is the intensity of characteristic peaks at 1592 and 1225 cm -1. The comparison of the second derivative IR spectra, as the second step of identification, shows that the characteristic absorption in 1400-1800 cm -1 is substantially different. The comparison of 2D-IR correlation spectra, as the third and final step of identification, can discriminate the liquors from another direction. Furthermore, the method was successfully applied to the discrimination of a counterfeit Moutai from the genuine Sauce liquor. The success of the three-step IR macro-fingerprint identification to provide a rapid and effective method for the identification of Chinese liquor suggests the potential extension of this technique to the identification and discrimination of other wine and spirits, as well.

Nonresonant Multiple-Pulse Control of Molecular Motions in Liquid

Directory of Open Access Journals (Sweden)

Nikiforov V.G.

2015-01-01

Full Text Available We propose the implementation of the multiple-pulse excitation for manipulation of the molecular contributions to the optically-heterodyne-detected optical-Kerr-effect. The key parameters controlling the specificity of the multiple-pulse excitation scenarios are the pulses durations, the delays between pulses, the relation between the pump pulses amplitudes and the pulses polarizations. We model the high-order optical responses and consider some principles of the scenarios construction. We show that it is possible to adjust the excitation scenario in such a way that the some responses can be removed from detected signal along with the enhancement of the interested response amplitude. The theoretical analysis and first experimental data reveal that the multiple-pulse excitation technique can be useful for the selective spectroscopy of the molecular vibrations and rotations in liquid.

Modeling the excitation of graphene plasmons in periodic grids of graphene ribbons: An analytical approach

DEFF Research Database (Denmark)

Gonçalves, P:A.D.; Dias, E. J. C.; Bludov, Yu V.

2016-01-01

We study electromagnetic scattering and subsequent plasmonic excitations in periodic grids of graphene ribbons. To address this problem, we develop an analytical method to describe the plasmon-assisted absorption of electromagnetic radiation by a periodic structure of graphene ribbons forming...... a diffraction grating for THz and mid-IR light. The major advantage of this method lies in its ability to accurately describe the excitation of graphene surface plasmons (GSPs) in one-dimensional (1D) graphene gratings without the use of both time-consuming, and computationally demanding full-wave numerical...... compare the theoretical data with spectra taken from experiments, for which we observe a very good agreement. These theoretical tools may therefore be applied to design new experiments and cutting-edge nanophotonic devices based on graphene plasmonics....

Excitation of Surface Plasmon Polaritons by Fluorescent Light from Organic Nanofibers

DEFF Research Database (Denmark)

Sobolewska, Elżbieta Karolina; Jozefowski, Leszek; Kawalec, Tomasz

2017-01-01

-coherent excitation indicates its prospect for future integrated systems. To support our experimental results, we investigate the proposed geometries by analytical calculations and finite-difference-time-domain (FDTD) modelling. The experimentally obtained angular leakage radiation peak positions can readily...... be predicted by our analytical calculations. Nevertheless, the experimental results exhibit a distinct asymmetry in the peak intensities. In agreement with our FDTD calculations, we address this asymmetrical SPP excitation to the nanofiber molecular orientation. The proposed structure’s high flexibility...

Molecular spectroscopy

International Nuclear Information System (INIS)

Kokh, Eh.; Zonntag, B.

1981-01-01

The latest investigation results on molecular spectroscopy with application of synchrotron radiation in the region of vacuum ultraviolet are generalized. Some results on investigation of excited, superexcited and ionized molecule states with the use of adsorption spectroscopy, photoelectron spectroscopy, by fluorescent and mass-spectrometric methods are considered [ru

Identification of Serine Conformers by Matrix-Isolation IR Spectroscopy Aided by Near-Infrared Laser Induced Conformational Change, 2D Correlation Analysis, and Quantum Mechanical Anharmonic Computations

Science.gov (United States)

Najbauer, Eszter E.; Bazsó, Gábor; Apóstolo, Rui; Fausto, Rui; Biczysko, Malgorzata; Barone, Vincenzo; Tarczay, György

2018-01-01

The conformers of α-serine were investigated by matrix-isolation IR spectroscopy combined with NIR laser irradiation. This method, aided by 2D correlation analysis, enabled unambiguously grouping the spectral lines to individual conformers. On the basis of comparison of at least nine experimentally observed vibrational transitions of each conformer with empirically scaled (SQM) and anharmonic (GVPT2) computed IR spectra, 6 conformers were identified. In addition, the presence of at least one more conformer in Ar matrix was proved, and a short-lived conformer with a half-live of (3.7±0.5)·103 s in N2 matrix was generated by NIR irradiation. The analysis of the NIR laser induced conversions revealed that the excitation of the stretching overtone of both the side-chain and the carboxylic OH groups can effectively promote conformational changes, but remarkably different paths were observed for the two kinds of excitations. PMID:26201050

Excitation of isomeric states 1h11/2 in (γ, n) reactions

International Nuclear Information System (INIS)

Tonchev, A.P.; Gangrskij, Yu.P.; Belov, A.G.

1995-01-01

The cross sections of (γ, n) reactions were measured for ground and isomeric states 1h 11/2 in 16 isotopes of Pd, Cd, Sn, Te, Ba, Ce, Nd and Sm. The energy of γ-rays was placed in the region of Giant Dipole Resonance. An activation method of measurements has been used. IR dependence of neutron and proton number in nucleus was detected and of excitation energy of residual nucleus as well. Different factors influencing the values of the isomeric ratios are discussed. 20 refs., 5 figs., 2 tabs

Selective two-photon excitation of a vibronic state by correlated photons.

Science.gov (United States)

Oka, Hisaki

2011-03-28

We theoretically investigate the two-photon excitation of a molecular vibronic state by correlated photons with energy anticorrelation. A Morse oscillator having three sets of vibronic states is used, as an example, to evaluate the selectivity and efficiency of two-photon excitation. We show that a vibrational mode can be selectively excited with high efficiency by the correlated photons, without phase manipulation or pulse-shaping techniques. This can be achieved by controlling the quantum correlation so that the photon pair concurrently has two pulse widths, namely, a temporally narrow width and a spectrally narrow width. Though this concurrence is seemingly contradictory, we can create such a photon pair by tailoring the quantum correlation between two photons.

Can Measured Synergy Excitations Accurately Construct Unmeasured Muscle Excitations?

Science.gov (United States)

Bianco, Nicholas A; Patten, Carolynn; Fregly, Benjamin J

2018-01-01

Accurate prediction of muscle and joint contact forces during human movement could improve treatment planning for disorders such as osteoarthritis, stroke, Parkinson's disease, and cerebral palsy. Recent studies suggest that muscle synergies, a low-dimensional representation of a large set of muscle electromyographic (EMG) signals (henceforth called "muscle excitations"), may reduce the redundancy of muscle excitation solutions predicted by optimization methods. This study explores the feasibility of using muscle synergy information extracted from eight muscle EMG signals (henceforth called "included" muscle excitations) to accurately construct muscle excitations from up to 16 additional EMG signals (henceforth called "excluded" muscle excitations). Using treadmill walking data collected at multiple speeds from two subjects (one healthy, one poststroke), we performed muscle synergy analysis on all possible subsets of eight included muscle excitations and evaluated how well the calculated time-varying synergy excitations could construct the remaining excluded muscle excitations (henceforth called "synergy extrapolation"). We found that some, but not all, eight-muscle subsets yielded synergy excitations that achieved >90% extrapolation variance accounted for (VAF). Using the top 10% of subsets, we developed muscle selection heuristics to identify included muscle combinations whose synergy excitations achieved high extrapolation accuracy. For 3, 4, and 5 synergies, these heuristics yielded extrapolation VAF values approximately 5% lower than corresponding reconstruction VAF values for each associated eight-muscle subset. These results suggest that synergy excitations obtained from experimentally measured muscle excitations can accurately construct unmeasured muscle excitations, which could help limit muscle excitations predicted by muscle force optimizations.

Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

Science.gov (United States)

Uma Maheswari, J; Muthu, S; Sundius, Tom

2014-04-05

A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths λmax were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed. Copyright © 2014 Elsevier B.V. All rights reserved.

Excited-state intramolecular hydrogen transfer (ESIHT) of 1,8-Dihydroxy-9,10-anthraquinone (DHAQ) characterized by ultrafast electronic and vibrational spectroscopy and computational modeling

KAUST Repository

Mohammed, Omar F.; Xiao, Dequan; Batista, Victor S.; Nibbering, Erik Theodorus Johannes

2014-01-01

of femtosecond UV/vis and UV/IR pump-probe spectroscopic data. Upon photoabsorption at 400 nm, the S 2 electronic excited state is initially populated, followed by a rapid equilibration within 150 fs through population transfer to the S 1 state where DHAQ

The Introduction of an Undergraduate Interventional Radiology (IR) Curriculum: Impact on Medical Student Knowledge and Interest in IR

International Nuclear Information System (INIS)

Shaikh, M.; Shaygi, B.; Asadi, H.; Thanaratnam, P.; Pennycooke, K.; Mirza, M.; Lee, M.

2016-01-01

IntroductionInterventional radiology (IR) plays a vital role in modern medicine, with increasing demand for services, but with a shortage of experienced interventionalists. The aim of this study was to determine the impact of a recently introduced IR curriculum on perception, knowledge, and interest of medical students regarding various aspects of IR.MethodsIn 2014, an anonymous web-based questionnaire was sent to 309 4th year medical students in a single institution within an EU country, both before and after delivery of a 10-h IR teaching curriculum.ResultsSeventy-six percent (236/309) of the respondents participated in the pre-IR module survey, while 50 % (157/309) responded to the post-IR module survey. While 62 % (147/236) of the respondents reported poor or no knowledge of IR compared to other medical disciplines in the pre-IR module survey, this decreased to 17 % (27/157) in the post-IR module survey. The correct responses regarding knowledge of selected IR procedures improved from 70 to 94 % for venous access, 78 to 99 % for uterine fibroid embolization, 75 to 97 % for GI bleeding embolization, 60 to 92 % for trauma embolization, 71 to 92 % for tumor ablation, and 81 to 94 % for angioplasty and stenting in peripheral arterial disease. With regard to knowledge of IR clinical roles, responses improved from 42 to 59 % for outpatient clinic review of patients and having inpatient beds, 63–76 % for direct patient consultation, and 43–60 % for having regular ward rounds. The number of students who would consider a career in IR increased from 60 to 73 %.ConclusionDelivering an undergraduate IR curriculum increased the knowledge and understanding of various aspects of IR and also the general enthusiasm for pursuing this specialty as a future career choice.

The Introduction of an Undergraduate Interventional Radiology (IR) Curriculum: Impact on Medical Student Knowledge and Interest in IR

Energy Technology Data Exchange (ETDEWEB)

Shaikh, M. [Bradford Royal Infirmary, Department of Radiology, Bradford Teaching Hospital Foundation Trust (United Kingdom); Shaygi, B. [Royal Devon and Exeter Hospital, Interventional Radiology Department (United Kingdom); Asadi, H., E-mail: asadi.hamed@gmail.com; Thanaratnam, P.; Pennycooke, K.; Mirza, M.; Lee, M., E-mail: mlee@rcsi.ie [Beaumont Hospital, Interventional Radiology Service, Department of Radiology (Ireland)

2016-04-15

IntroductionInterventional radiology (IR) plays a vital role in modern medicine, with increasing demand for services, but with a shortage of experienced interventionalists. The aim of this study was to determine the impact of a recently introduced IR curriculum on perception, knowledge, and interest of medical students regarding various aspects of IR.MethodsIn 2014, an anonymous web-based questionnaire was sent to 309 4th year medical students in a single institution within an EU country, both before and after delivery of a 10-h IR teaching curriculum.ResultsSeventy-six percent (236/309) of the respondents participated in the pre-IR module survey, while 50 % (157/309) responded to the post-IR module survey. While 62 % (147/236) of the respondents reported poor or no knowledge of IR compared to other medical disciplines in the pre-IR module survey, this decreased to 17 % (27/157) in the post-IR module survey. The correct responses regarding knowledge of selected IR procedures improved from 70 to 94 % for venous access, 78 to 99 % for uterine fibroid embolization, 75 to 97 % for GI bleeding embolization, 60 to 92 % for trauma embolization, 71 to 92 % for tumor ablation, and 81 to 94 % for angioplasty and stenting in peripheral arterial disease. With regard to knowledge of IR clinical roles, responses improved from 42 to 59 % for outpatient clinic review of patients and having inpatient beds, 63–76 % for direct patient consultation, and 43–60 % for having regular ward rounds. The number of students who would consider a career in IR increased from 60 to 73 %.ConclusionDelivering an undergraduate IR curriculum increased the knowledge and understanding of various aspects of IR and also the general enthusiasm for pursuing this specialty as a future career choice.

Energy transfer in diatom/diatom molecular collisions

International Nuclear Information System (INIS)

Sohlberg, K.W.

1992-01-01

In a collision of two molecules, the translational energy of the collision may be redistributed into internal energy of rotation, vibration, or electron motion, in one or both of the colliding partners. In addition, internal energy in one or more of these modes may be open-quotes quenchedclose quotes into translation, leading to a superelastic collision. Such energy transfer may take place by a number of mechanisms. This energy transfer is of fundamental importance in understanding chemical reaction dynamics. Nearly all chemical reactions take place through a bimolecular collision process (or multiple bimolecular collisions) and the quantum state specificity of the reaction can have a major role in determining the kinetics of the reaction, In particular, the author has investigated vibrational energy transfer in collisions between two diatomic molecules. In addition to serving as models for all molecular collision process, gas phase collisions of these species are ubiquitous in atmospheric phenomena which are of critical importance in answering the current questions about the human induced degradation of the earth's atmospheric. Classical trajectory methods have been used to explore the excitation of vibrations in gas-phase collisions of the nitrogen molecular ion with its parent molecule. The near symmetry of the reactants is shown to result in a high probability that the two molecules are excited by an equal amount of energy. This provides a possible explanation of the molecular beam measurements which show that the total number of vibrational energy quanta excited in the collision is, with a high probability that the two molecules are excited by an equal amount of energy. This provides a possible explanation of the molecular beam measurements which show that the total number of vibrational energy quanta excited in the collision is, with a high probability, even

Ion beam synthesis of IrSi3 by implantation of 2 MeV Ir ions

International Nuclear Information System (INIS)

Sjoreen, T.P.; Chisholm, M.F.; Hinneberg, H.J.

1992-11-01

Formation of a buried IrSi 3 layer in (111) oriented Si by ion implantation and annealing has been studied at an implantation energy of 2 MeV for substrate temperatures of 450--550C. Rutherford backscattering (RBS), ion channeling and cross-sectional transmission electron microscopy showed that a buried epitaxial IrSi 3 layer is produced at 550C by implanting ≥ 3.4 x 10 17 Ir/cm 2 and subsequently annealing for 1 h at 1000C plus 5 h at 1100C. At a dose of 3.4 x 10 17 Ir/cm 2 , the thickness of the layer varied between 120 and 190 nm and many large IrSi 3 precipitates were present above and below the film. Increasing the dose to 4.4 x 10 17 Ir/cm 2 improved the layer uniformity at the expense of increased lattice damage in the overlying Si. RBS analysis of layer formation as a function of substrate temperature revealed the competition between the mechanisms for optimizing surface crystallinity vs. IrSi 3 layer formation. Little apparent substrate temperature dependence was evident in the as-implanted state but after annealing the crystallinity of the top Si layer was observed to deteriorate with increasing substrate temperature while the precipitate coarsening and coalescence improved

Smulkaus ir vidutinio verslo konkurencingumas Lietuvoje

OpenAIRE

Vijeikis, Juozas; Makštutis, Antanas

2009-01-01

Straipsnio mokslinė problema, naujumas ir aktualumas. Konkurencingumas kaip įmonių efektyvios veiklos reiškinys yra aktualus šalies verslo gyvenime vykdant darnios ekonominės plėtros politiką. Ši politika kaip problema smulkaus ir vidutinio verslo (SVV) plėtrai ir konkurencingumui didinti nėra sistemiškai ištirta ir aprašyta Lietuvos sąlygomis mokslinėje ir praktinėje literatūroje. Vienas svarbiausių veiksnių, siekiant spartaus ekonominio augimo, yra darnios verslininkystės plėtra Lietuvoje n...

Structural, phase stability, electronic, elastic properties and hardness of IrN{sub 2} and zinc blende IrN: First-principles calculations

Energy Technology Data Exchange (ETDEWEB)

Zhou, Zhaobo [Key Laboratory of Advanced Materials of Yunnan Province & Key Laboratory of Advanced Materials of Non-Ferrous and Precious Rare Metals Ministry of Education, Kunming University of Science and Technology, Kunming 650093 (China); Zhou, Xiaolong, E-mail: kmzxlong@163.com [Key Laboratory of Advanced Materials of Yunnan Province & Key Laboratory of Advanced Materials of Non-Ferrous and Precious Rare Metals Ministry of Education, Kunming University of Science and Technology, Kunming 650093 (China); Zhang, Kunhua [State Key Laboratory of Rare Precious Metals Comprehensive Utilization of New Technologies, Kunming Institute of Precious Metals, Kunming 650106 (China)

2016-12-15

First-principle calculations were performed to investigate the structural, phase stability, electronic, elastic properties and hardness of monoclinic structure IrN{sub 2} (m-IrN{sub 2}), orthorhombic structure IrN{sub 2} (o-IrN{sub 2}) and zinc blende structure IrN (ZB IrN). The results show us that only m-IrN{sub 2} is both thermodynamic and dynamic stability. The calculated band structure and density of states (DOS) curves indicate that o-IrN{sub 2} and ZB Ir-N compounds we calculated have metallic behavior while m-IrN{sub 2} has a small band gap of ~0.3 eV, and exist a common hybridization between Ir-5d and N-2p states, which forming covalent bonding between Ir and N atoms. The difference charge density reveals the electron transfer from Ir atom to N atom for three Ir-N compounds, which forming strong directional covalent bonds. Notable, a strong N-N bond appeared in m-IrN{sub 2} and o-IrN{sub 2}. The ratio of bulk to shear modulus (B/G) indicate that three Ir-N compounds we calculated are ductile, and ZB IrN possesses a better ductility than two types IrN{sub 2}. m-IrN{sub 2} has highest Debye temperature (736 K), illustrating it possesses strongest covalent bonding. The hardness of three Ir-N compounds were also calculated, and the results reveal that m-IrN{sub 2} (18.23 GPa) and o-IrN{sub 2} (18.02 GPa) are ultraincompressible while ZB IrN has a negative value, which may be attributed to phase transition at ca. 1.98 GPa.

Total photoionization cross-sections of excited electronic states by the algebraic diagrammatic construction-Stieltjes-Lanczos method.

Science.gov (United States)

Ruberti, M; Yun, R; Gokhberg, K; Kopelke, S; Cederbaum, L S; Tarantelli, F; Averbukh, V

2014-05-14

Here, we extend the L2 ab initio method for molecular photoionization cross-sections introduced in Gokhberg et al. [J. Chem. Phys. 130, 064104 (2009)] and benchmarked in Ruberti et al. [J. Chem. Phys. 139, 144107 (2013)] to the calculation of total photoionization cross-sections of molecules in electronically excited states. The method is based on the ab initio description of molecular electronic states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. The intermediate state representation of the dipole operator in the ADC basis is used to compute the transition moments between the excited states of the molecule. We compare the results obtained using different levels of the many-body theory, i.e., ADC(1), ADC(2), and ADC(2)x for the first two excited states of CO, N2, and H2O both at the ground state and the excited state equilibrium or saddle point geometries. We find that the single excitation ADC(1) method is not adequate even at the qualitative level and that the inclusion of double electronic excitations for description of excited state photoionization is essential. Moreover, we show that the use of the extended ADC(2)x method leads to a substantial systematic difference from the strictly second-order ADC(2). Our calculations demonstrate that a theoretical modelling of photoionization of excited states requires an intrinsically double excitation theory with respect to the ground state and cannot be achieved by the standard single excitation methods with the ground state as a reference.

Cryogenic exciter

Science.gov (United States)

Bray, James William [Niskayuna, NY; Garces, Luis Jose [Niskayuna, NY

2012-03-13

The disclosed technology is a cryogenic static exciter. The cryogenic static exciter is connected to a synchronous electric machine that has a field winding. The synchronous electric machine is cooled via a refrigerator or cryogen like liquid nitrogen. The static exciter is in communication with the field winding and is operating at ambient temperature. The static exciter receives cooling from a refrigerator or cryogen source, which may also service the synchronous machine, to selected areas of the static exciter and the cooling selectively reduces the operating temperature of the selected areas of the static exciter.

Clusterin: an IR-inducible protein determining life and death

Energy Technology Data Exchange (ETDEWEB)

DAVID A. BOOTHMAN, Ph.D.

2006-07-11

The roles of ionizing radiation (IR)-inducible genes/proteins are now being elucidated and the research team will focus on the functions of the clusterin (CLU) proteins after low dose IR exposures. With funding from the DOE, we discovered that x-ray-inducible transcript/protein #8 (xip8) bound to the Ku70 DNA double strand break repair protein using various molecular biology techniques. We showed that translation of the CLU/xip8 transcript was complicated, leading to two classes of proteins separated by their intracellular processing. One set of CLU proteins (a secreted and precursor protein, sCLU and psCLU, respectively) were induced by very low doses of IR (>2.0 cGy) and subsequently secreted from the cell. The functions of sCLU, particularly in bystander effects, are not known; sCLU does not bind Ku70, but can interact with the TGF-ß II receptor. Another intracellular class of CLU proteins was targeted to the cytoplasm and existed in a dormant precursor nuclear form (pnCLU). After higher IR doses (>1.0 Gy), pnCLU was activated via post-translational modification, and translocated to the nucleus, where nuclear CLU (nCLU) interacted with Ku70/Ku80, and signaled cell death. The mechanism(s) of how cells die following nCLU accumulation are unknown. Recent data from our lab indicate that CLU gene transcription is also complicated. Thus far, the data suggest that: (a) p53 is a negative regulator of CLU transcription, however, the mechanisms by which it exerts this negative pressure are not known; and (b) IR induces transcription of the CLU promoter, independent of p53, at regulatory elements that lie between -1403 and -325 bps 5'-from the TATAA box. In this renewal, the research team will investigate three separate, but interrelated hypotheses: (1) p53 negatively regulates the CLU promoter via distinct head to tail p53 half sites, and induction is mediated by the combination of retinoblatoma control elements (RCEs) and NF-∫B sites; (2) sCLU is cytoprotective

Clusterin: an IR-inducible protein determining life and death

International Nuclear Information System (INIS)

DAVID A. BOOTHMAN

2006-01-01

The roles of ionizing radiation (IR)-inducible genes/proteins are now being elucidated and the research team will focus on the functions of the clusterin (CLU) proteins after low dose IR exposures. With funding from the DOE, we discovered that x-ray-inducible transcript/protein No.8 (xip8) bound to the Ku70 DNA double strand break repair protein using various molecular biology techniques. We showed that translation of the CLU/xip8 transcript was complicated, leading to two classes of proteins separated by their intracellular processing. One set of CLU proteins (a secreted and precursor protein, sCLU and psCLU, respectively) were induced by very low doses of IR (>2.0 cGy) and subsequently secreted from the cell. The functions of sCLU, particularly in bystander effects, are not known; sCLU does not bind Ku70, but can interact with the TGF-? II receptor. Another intracellular class of CLU proteins was targeted to the cytoplasm and existed in a dormant precursor nuclear form (pnCLU). After higher IR doses (>1.0 Gy), pnCLU was activated via post-translational modification, and translocated to the nucleus, where nuclear CLU (nCLU) interacted with Ku70/Ku80, and signaled cell death. The mechanism(s) of how cells die following nCLU accumulation are unknown. Recent data from our lab indicate that CLU gene transcription is also complicated. Thus far, the data suggest that: (a) p53 is a negative regulator of CLU transcription, however, the mechanisms by which it exerts this negative pressure are not known; and (b) IR induces transcription of the CLU promoter, independent of p53, at regulatory elements that lie between -1403 and -325 bps 5'-from the TATAA box. In this renewal, the research team will investigate three separate, but interrelated hypotheses: (1) p53 negatively regulates the CLU promoter via distinct head to tail p53 half sites, and induction is mediated by the combination of retinoblatoma control elements (RCEs) and NF-?B sites; (2) sCLU is cytoprotective and

Protection of p+-n-Si Photoanodes by Sputter-Deposited Ir/IrOxThin Films

DEFF Research Database (Denmark)

Mei, Bastian Timo; Seger, Brian; Pedersen, Thomas

2014-01-01

Sputter deposition of Ir/IrOx on p+-n-Si without interfacial corrosion protection layers yielded photoanodes capable of efficient water oxidation (OER) in acidic media (1 M H2SO4). Stability of at least 18 h was shown by chronoamperomety at 1.23 V versus RHE (reversible hydrogen electrode) under 38...... density of 1 mA/cm2 at 1.05 V vs. RHE. Further improvement by heat treatment resulted in a cathodic shift of 40 mV and enabled a current density of 10 mA/cm2 (requirements for a 10% efficient tandem device) at 1.12 V vs. RHS under irradiation. Thus, the simple IrOx/Ir/p+-n-Si structures not only provide...

Electrical properties of molecular crystals

International Nuclear Information System (INIS)

Barraud, A.

1968-01-01

This literature survey summarizes the electrical properties of molecular crystals: molecular crystal structure, transport and excitation mechanisms of charge-carriers, and differences compared to inorganic semi-conductors. The main results concerning the electrical conductivity of the most-studied molecular crystals are presented, together with the optical and photo-electrical properties of these crystals. Finally the different types of electrical measurements used are reviewed, as well as the limits of each method. (author) [fr

Vibration-rotation band intensities in the IR spectra of polyatomic molecules

International Nuclear Information System (INIS)

El'kin, M.D.; Kosterina, E.K.; Berezin

1995-01-01

Using the curvilinear vibrational coordinates for a nuclear subsystem, expressions for the effective dipole-moment operators are derived in order to analyze the vibrational-rotational transitions in the IR spectra of polyatomic rigid molecules. The explicit expressions obtained for the intensities of hot bands allow one to estimate the influence of the vibration-rotation interaction within the framework of the adopted molecular-vibration model. The suggested method is shown to be suitable for Raman spectra analysis. 12 refs

Novel cross-talk between IGF-IR and DDR1 regulates IGF-IR trafficking, signaling and biological responses

Science.gov (United States)

Sacco, Antonella; Morcavallo, Alaide; Vella, Veronica; Voci, Concetta; Spatuzza, Michela; Xu, Shi-Qiong; Iozzo, Renato V.; Vigneri, Riccardo; Morrione, Andrea; Belfiore, Antonino

2015-01-01

The insulin-like growth factor-I receptor (IGF-IR), plays a key role in regulating mammalian development and growth, and is frequently deregulated in cancer contributing to tumor initiation and progression. Discoidin domain receptor 1 (DDR1), a collagen receptor tyrosine-kinase, is as well frequently overexpressed in cancer and implicated in cancer progression. Thus, we investigated whether a functional cross-talk between the IGF-IR and DDR1 exists and plays any role in cancer progression. Using human breast cancer cells we found that DDR1 constitutively associated with the IGF-IR. However, this interaction was enhanced by IGF-I stimulation, which promoted rapid DDR1 tyrosine-phosphorylation and co-internalization with the IGF-IR. Significantly, DDR1 was critical for IGF-IR endocytosis and trafficking into early endosomes, IGF-IR protein expression and IGF-I intracellular signaling and biological effects, including cell proliferation, migration and colony formation. These biological responses were inhibited by DDR1 silencing and enhanced by DDR1 overexpression. Experiments in mouse fibroblasts co-transfected with the human IGF-IR and DDR1 gave similar results and indicated that, in the absence of IGF-IR, collagen-dependent phosphorylation of DDR1 is impaired. These results demonstrate a critical role of DDR1 in the regulation of IGF-IR action, and identify DDR1 as a novel important target for breast cancers that overexpress IGF-IR. PMID:25840417

Metal ion sequestration: An exciting dimension for molecularly ...

African Journals Online (AJOL)

The use of a tight binding macrocyclic ligand to complex a metal ion so that this serves as receptee on the Molecularly Imprinted Polymer (MIP) receptor as described here affords a sequestration route for a targeted metal ion, with potential for environmental remediation and restoration applications. Ethylene glycol ...

Construction and characterization on composite electrospinning fibers doped with iridium complex owing fluorine atoms in its auxiliary ligand.

Science.gov (United States)

Gao, Yu-Qian; Zhang, Shimin; Wang, Pengju; Xu, Shuxia; Wu, Kun; Mou, Wanzhi

2014-10-15

The authors synthesized a fluorine-containing Ir(III) complex Ir(PTZ)2(HFD) and the corresponding composite electrospinning fibers PVP@Ir(PTZ)2(HFD), where PTZ, HFD and PVP stood for 2-phenylbenzo[d]thiazole, 1,1,1,5,5,5-hexafluoropentane-2,4-dione and poly(vinylpyrrolidone), respectively. The molecular structure of the Ir(III) complex was confirmed by its single crystal analysis, which suggested that Ir(PTZ)2(HFD) molecules crystallized as monoclinic system with two molecules in each unit cell. Density functional theory calculation on the crystal revealed that the onset electronic transitions possessed a mixed character of metal-to-ligand-charge-transfer (MLCT) and ligand-to-ligand-charge-transfer (LLCT). Ir(PTZ)2(HFD) was then doped into electrospinning fibers so that the photophysical comparison between bulk Ir(PTZ)2(HFD) and composite samples could be performed. It was found that both face-to-face π-π attraction in crystal and the immobilization in PVP host could improve photoluminescence performance by restraining the geometric relaxation of MLCT excited state, showing emission blue shift, longer excited state lifetime and improved photostability. Copyright © 2014 Elsevier B.V. All rights reserved.

Mid-infrared, long wave infrared (4-12 μm) molecular emission signatures from pharmaceuticals using laser-induced breakdown spectroscopy (LIBS).

Science.gov (United States)

Yang, Clayton S-C; Brown, Ei E; Kumi-Barimah, Eric; Hommerich, Uwe H; Jin, Feng; Trivedi, Sudhir B; Samuels, Alan C; Snyder, A Peter

2014-01-01

In an effort to augment the atomic emission spectra of conventional laser-induced breakdown spectroscopy (LIBS) and to provide an increase in selectivity, mid-wave to long-wave infrared (IR), LIBS studies were performed on several organic pharmaceuticals. Laser-induced breakdown spectroscopy signature molecular emissions of target organic compounds are observed for the first time in the IR fingerprint spectral region between 4-12 μm. The IR emission spectra of select organic pharmaceuticals closely correlate with their respective standard Fourier transform infrared spectra. Intact and/or fragment sample molecular species evidently survive the LIBS event. The combination of atomic emission signatures derived from conventional ultraviolet-visible-near-infrared LIBS with fingerprints of intact molecular entities determined from IR LIBS promises to be a powerful tool for chemical detection.

Charge-transfer state excitation as the main mechanism of the photodarkening process in ytterbium-doped aluminosilicate fibres

Energy Technology Data Exchange (ETDEWEB)

Bobkov, K K; Rybaltovsky, A A; Vel' miskin, V V; Likhachev, M E; Bubnov, M M; Dianov, E M [Fiber Optics Research Center, Russian Academy of Sciences, Moscow (Russian Federation); Umnikov, A A; Gur' yanov, A N; Vechkanov, N N [G.G.Devyatykh Institute of Chemistry of High-Purity Substances, Russian Academy of Sciences, Nizhnii Novgorod (Russian Federation); Shestakova, I A [Open Joint-Stock Company M.F. Stel' makh Polyus Research Institute, Moscow (Russian Federation)

2014-12-31

We have studied photodarkening in ytterbium-doped fibre preforms with an aluminosilicate glass core. Analysis of their absorption and luminescence spectra indicates the formation of stable Yb{sup 2+} ions in the glass network under IR laser pumping at a wavelength λ = 915 nm and under UV irradiation with an excimer laser (λ = 193 nm). We have performed comparative studies of the luminescence spectra of the preforms and crystals under excitation at a wavelength of 193 nm. The mechanism behind the formation of Yb{sup 2+} ions and aluminium – oxygen hole centres (Al-OHCs), common to ytterbium-doped YAG crystals and aluminosilicate glass, has been identified: photoinduced Yb{sup 3+} charge-transfer state excitation. (optical fibres)

Excited-state relaxation of some aminoquinolines

Directory of Open Access Journals (Sweden)

2006-01-01

Full Text Available The absorption and fluorescence spectra, fluorescence quantum yields and lifetimes, and fluorescence rate constants ( k f of 2-amino-3-( 2 ′ -benzoxazolylquinoline (I, 2-amino-3-( 2 ′ -benzothiazolylquinoline (II, 2-amino-3-( 2 ′ -methoxybenzothiazolyl-quinoline (III, 2-amino-3-( 2 ′ -benzothiazolylbenzoquinoline (IV at different temperatures have been measured. The shortwavelength shift of fluorescence spectra of compounds studied (23–49 nm in ethanol as the temperature decreases (the solvent viscosity increases points out that the excited-state relaxation process takes place. The rate of this process depends essentially on the solvent viscosity, but not the solvent polarity. The essential increasing of fluorescence rate constant k f (up to about 7 times as the solvent viscosity increases proves the existence of excited-state structural relaxation consisting in the mutual internal rotation of molecular fragments of aminoquinolines studied, followed by the solvent orientational relaxation.

Exon silencing by UAGG motifs in response to neuronal excitation.

Directory of Open Access Journals (Sweden)

Ping An

2007-02-01

Full Text Available Alternative pre-mRNA splicing plays fundamental roles in neurons by generating functional diversity in proteins associated with the communication and connectivity of the synapse. The CI cassette of the NMDA R1 receptor is one of a variety of exons that show an increase in exon skipping in response to cell excitation, but the molecular nature of this splicing responsiveness is not yet understood. Here we investigate the molecular basis for the induced changes in splicing of the CI cassette exon in primary rat cortical cultures in response to KCl-induced depolarization using an expression assay with a tight neuron-specific readout. In this system, exon silencing in response to neuronal excitation was mediated by multiple UAGG-type silencing motifs, and transfer of the motifs to a constitutive exon conferred a similar responsiveness by gain of function. Biochemical analysis of protein binding to UAGG motifs in extracts prepared from treated and mock-treated cortical cultures showed an increase in nuclear hnRNP A1-RNA binding activity in parallel with excitation. Evidence for the role of the NMDA receptor and calcium signaling in the induced splicing response was shown by the use of specific antagonists, as well as cell-permeable inhibitors of signaling pathways. Finally, a wider role for exon-skipping responsiveness is shown to involve additional exons with UAGG-related silencing motifs, and transcripts involved in synaptic functions. These results suggest that, at the post-transcriptional level, excitable exons such as the CI cassette may be involved in strategies by which neurons mount adaptive responses to hyperstimulation.

HOMA1-IR and HOMA2-IR indexes in identifying insulin resistance and metabolic syndrome: Brazilian Metabolic Syndrome Study (BRAMS).

Science.gov (United States)

Geloneze, Bruno; Vasques, Ana Carolina Junqueira; Stabe, Christiane França Camargo; Pareja, José Carlos; Rosado, Lina Enriqueta Frandsen Paez de Lima; Queiroz, Elaine Cristina de; Tambascia, Marcos Antonio

2009-03-01

To investigate cut-off values for HOMA1-IR and HOMA2-IR to identify insulin resistance (IR) and metabolic syndrome (MS), and to assess the association of the indexes with components of the MS. Nondiabetic subjects from the Brazilian Metabolic Syndrome Study were studied (n = 1,203, 18 to 78 years). The cut-off values for IR were determined from the 90th percentile in the healthy group (n = 297) and, for MS, a ROC curve was generated for the total sample. In the healthy group, HOMA-IR indexes were associated with central obesity, triglycerides and total cholesterol (p 2.7 and HOMA2-IR > 1.8; and, for MS were: HOMA1-IR > 2.3 (sensitivity: 76.8%; specificity: 66.7%) and HOMA2-IR > 1.4 (sensitivity: 79.2%; specificity: 61.2%). The cut-off values identified for HOMA1-IR and HOMA2-IR indexes have a clinical and epidemiological application for identifying IR and MS in Westernized admixtured multi-ethnic populations.

IOT Overview: IR Instruments

Science.gov (United States)

Mason, E.

In this instrument review chapter the calibration plans of ESO IR instruments are presented and briefly reviewed focusing, in particular, on the case of ISAAC, which has been the first IR instrument at VLT and whose calibration plan served as prototype for the coming instruments.

Nonlinear optical sub-bandgap excitation of ZnO-based photonic resonators

Energy Technology Data Exchange (ETDEWEB)

Bader, Christina A.; Zeuner, Franziska; Bader, Manuel H. W.; Zentgraf, Thomas; Meier, Cedrik [Department of Physics and Center for Optoelectronics and Photonics Paderborn (CeOPP), Universität Paderborn, Warburger Str. 100, 33098 Paderborn (Germany)

2015-12-07

Zinc oxide (ZnO) is a versatile candidate for photonic devices due to its highly efficient optical emission. However, for pumping of ZnO photonic devices UV-sources are required. Here, we investigate the alternative usage of widely available pulsed near-infrared (NIR)-sources and compare the efficiency of linear and nonlinear excitation processes. We found that bulk ZnO, ZnO thin films grown by molecular beam epitaxy, and ZnO/SiO{sub 2} microdisk devices exhibit strong nonlinear response when excited with NIR pulses (λ ≈ 1060 nm). In addition, we show that the ZnO/SiO{sub 2} microdisks exhibit sharp whispering gallery modes over the blue-yellow part of the visible spectrum for both excitation conditions and high Q-factors up to Q = 4700. The results demonstrate that nonlinear excitation is an efficient way to pump ZnO photonic devices.

Atom condensation on an atomically smooth surface: Ir, Re, W, and Pd on Ir(111)

International Nuclear Information System (INIS)

Wang, S.C.; Ehrlich, G.

1991-01-01

The distribution of condensing metal atoms over the two types of sites present on an atomically smooth Ir(111) has been measured in a field ion microscope. For Ir, Re, W, and Pd from a thermal source, condensing on Ir(111) at ∼20 K, the atoms are randomly distributed, as expected if they condense at the first site struck

Synthesis and IR spectral study of MoO2Cl2 molecular complex with acetoacetanilides. Crystal structure of MoO2Cl2 complex with acetoacet-2-toluidine

International Nuclear Information System (INIS)

Abramenko, V.L.; Sergienko, V.S.; Churakov, A.V.

2000-01-01

Certain MoO 2 Cl 2 complexes with acetoacetanilide derivatives were synthesized, two IR spectral study being performed. Crystal and molecular structure of MoO 2 Cl 2 complex with acetoacet-2-toluidine (HL) was determined using X-ray diffraction analysis. The crystals are monoclinic, a = 7.621 (7), b = 9.498 (3), c = 19.980 (9) A, β = 95.16 (7), Z = 4, sp.gr. P2 1 /n. Coordination polyhedron of Mo atom is a distorted octahedron with two O oxoatoms in cis-position, two Cl atom in mutual trans-position and two O(HL) atoms in trans-positions in reference to O(oxo) [ru

16O+16O molecular nature of the superdeformed band of 32S and the evolution of the molecular structure

International Nuclear Information System (INIS)

Kimura, Masaaki; Horiuchi, Hisashi

2004-01-01

The relation between the superdeformed band of 32 S and 16 O+ 16 O molecular bands is studied by the deformed-basis antisymmetrized molecular dynamics with the Gogny D1S force. It is found that the obtained superdeformed band members of S have a considerable amount of the 16 O+ 16 O component. Above the superdeformed band, we have obtained two excited rotational bands which have more prominent character of the 16 O+ 16 O molecular band. These three rotational bands are regarded as a series of 16 O+ 16 O molecular bands which were predicted by using the unique 16 O- 16 O optical potential. As the excitation energy and principal quantum number of the relative motion increase, the 16 O+ 16 O cluster structure becomes more prominent but at the same time, the band members are fragmented into several states

Single-nucleotide polymorphism of INS, INSR, IRS1, IRS2, PPAR-G ...

Indian Academy of Sciences (India)

2017-03-02

Mar 2, 2017 ... Abstract. Polycystic ovary syndrome (PCOS) is the most common and a complex female endocrine disorder, and is one of the leading cause of female infertility. Here, we aimed to investigate the association of single-nucleotide polymorphism of INS, INSR,. IRS1, IRS2, PPAR-G and CAPN10 gene in the ...

Suppression of superconductivity in Nb by IrMn in IrMn/Nb bilayers

KAUST Repository

Wu, B. L.; Yang, Y. M.; Guo, Z. B.; Wu, Y. H.; Qiu, J. J.

2013-01-01

Effect of antiferromagnet on superconductivity has been investigated in IrMn/Nb bilayers. Significant suppression of both transition temperature (Tc) and lower critical field (Hc1) of Nb is found in IrMn/Nb bilayers as compared to a single layer Nb

Localized hole effects in inner-shell excitation

International Nuclear Information System (INIS)

Rescigno, T.N.; Orel, A.E.

1983-01-01

Ab initio calculations of valence shell ionization potentials have shown that orbital relaxation and correlation differences usually make contributions of comparable magnitude. In marked contrast to this observation is the situation for deep core ionization, where correlation differences (approx. 1 eV) play a relatively minor role compared to orbital relaxation (approx. 20 eV). Theoretical calculations have shown that this relaxation is most easily described if the 1s-vacancy created by a K-shell excitation is allowed to localize on one of the atomic centers. For molecules possessing a center of inversion, this means that the molecular orbitals that best describe the final state do not transform as any irreducible representation of the molecular point group. Recent experimental work by Shaw, King, Read and Cvejanovic and by Stefani and coworkers has prompted us to carry out further calculations on N 2 , as well as analogous investigations of 1s/sub N/ → π* excitation in NO and N 2 O. The generalized oscillator strengths display a striking similarity and point to the essential correctness of the localized hole picture for N 2 . The theoretical calculations are briefly described, followed by a summary of the results and comparison to experiment, followed by a short discussion

Encapsulation of 3-hydroxyflavone and fisetin in β-cyclodextrins: Excited state proton transfer fluorescence and molecular mechanics studies

Science.gov (United States)

Banerjee, Anwesha; Sengupta, Pradeep K.

2006-06-01

Excited-state intramolecular proton-transfer (ESIPT) and dual emission properties (emission profile, anisotropy and decay kinetics) of 3-hydroxyflavone (a synthetic, model flavonol) and fisetin (3,7,3',4'-OH-flavone, a therapeutically active plant flavonol) have been exploited to study their encapsulation in nano-cavities comprising of natural and chemically modified β-cyclodextrins. In the presence of β-CDs, both the flavonols show significantly enhanced relative yields (along with changes in other emission parameters) of the tautomer emission. In addition, for fisetin, large blue shifts are observed for the normal emission (which has significant charge transfer character). From these we infer that the flavonols are encaged in predominantly hydrophobic micro-environments, where external hydrogen bonding perturbations (interfering with the intrinsic ESIPT), and dipolar relaxation effects, are minimized. This is further explained from results of molecular mechanics calculations which indicate selectivity in orientation of the encapsulated flavonols. Moreover, chemical modification of the β-CDs is found to profoundly influence the binding affinities of the guest flavonols.

Insulin receptor substrates 1 and 2 but not Shc can activate the insulin receptor independent of insulin and induce proliferation in CHO-IR cells

International Nuclear Information System (INIS)

Niessen, Markus; Jaschinski, Frank; Item, Flurin; McNamara, Morgan P.; Spinas, Giatgen A.; Trueb, Thomas

2007-01-01

Ligand-activated insulin receptor (IR) attracts and phosphorylates various substrates such as insulin receptor substrates 1-4 (IRS) and Shc. To investigate how binding affinity for substrate affects signalling we generated chimeric receptors with the β-chain of the insulin receptor containing NPXY motives with different affinities for receptor substrates. We found that the extent of receptor tyrosine phosphorylation positively correlates with binding affinity towards IRS1/2 but not towards Shc. Moreover, overexpression of IRS1 or IRS2 but not of Shc increased IR tyrosine phosphorylation in a dose-dependent manner, also independent of insulin. Molecular truncations of IRS1 revealed that neither the isolated PH and PTB domains nor the C-terminus with the tyrosine phosphorylation sites alone are sufficient for substrate-dependent receptor activation. Overexpression of IRS1 and IRS2 impaired insulin-induced internalization of the IR in a dose-dependent manner suggesting that IRS proteins prevent endosome-associated receptor dephosphorylation/inactivation. IRS1 and IRS2 could therefore target the activated IR to different cellular compartments. Overexpression of IRS1 and IRS2 inhibited insulin-stimulated activation of the MAP kinases Erk1/2 while it increased/induced activation of Akt/PKB. Finally, overexpression of IRS1 and IRS2 but not of Shc induced DNA synthesis in starved CHO-IR cells independent of exogenous growth factors. Our results demonstrate that variations in cellular IRS1 and IRS2 concentration affect insulin signalling both upstream and downstream and that IRS proteins could play instructive rather than just permissive roles in signal transmission

On formation mechanism of Pd-Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

Science.gov (United States)

Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

2013-10-01

The formation mechanism of Pd-Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH3)4][IrCl6] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd-Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10-200 nm) and dendrite Ir-rich (10-50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd-Ir nanoparticles, were found to occur.

On formation mechanism of Pd–Ir bimetallic nanoparticles through thermal decomposition of [Pd(NH3)4][IrCl6

International Nuclear Information System (INIS)

Asanova, Tatyana I.; Asanov, Igor P.; Kim, Min-Gyu; Gerasimov, Evgeny Yu.; Zadesenets, Andrey V.; Plyusnin, Pavel E.; Korenev, Sergey V.

2013-01-01

The formation mechanism of Pd–Ir nanoparticles during thermal decomposition of double complex salt [Pd(NH 3 ) 4 ][IrCl 6 ] has been studied by in situ X-ray absorption (XAFS) and photoelectron (XPS) spectroscopies. The changes in the structure of the Pd and Ir closest to the surroundings and chemical states of Pd, Ir, Cl, and N atoms were traced in the range from room temperature to 420 °C in inert atmosphere. It was established that the thermal decomposition process is carried out in 5 steps. The Pd–Ir nanoparticles are formed in pyramidal/rounded Pd-rich (10–200 nm) and dendrite Ir-rich (10–50 nm) solid solutions. A d charge depletion at Ir site and a gain at Pd, as well as the intra-atomic charge redistribution between the outer d and s and p electrons of both Ir and Pd in Pd–Ir nanoparticles, were found to occur.Graphical Abstract

FT-IR spectroscopic analyses of 2-(2-furanylmethylene) propanedinitrile

Science.gov (United States)

Soliman, H. S.; Eid, Kh. M.; Ali, H. A. M.; El-Mansy, M. A. M.; Atef, S. M.

2013-03-01

In the present work, a computational study for the optimized molecular structural parameters, thermo-chemical parameters, total dipole moment, HOMO-LUMO energy gap and a combined experimental and computational study for FT-IR spectra for 2-(2-furanylmethylene) propanedinitrile have been investigated using B3LYP utilizing 6-31G and 6-311G basis set. Our calculated results showed that the investigated compound possesses a dipole moment of 7.5 D and HOMO-LUMO energy gap of 3.92 eV using B3LYP/6-311G which indicates that our investigated compound is highly applicable for photovoltaic solar cell applications.

Study of interactions of an anticancer drug neratinib with bovine serum albumin: Spectroscopic and molecular docking approach

Science.gov (United States)

Wani, Tanveer A.; Bakheit, Ahmed H.; Abounassif, M. A.; Zargar, Seema

2018-03-01

Binding of therapeutic agents to plasma proteins, particularly to serum albumin, provides valuable information in the drug development. This study was designed to evaluate the binding interaction of neratinib with bovine serum albumin (BSA). Neratinib blocks HER2 signaling and is effective in trastuzumab-resistant breast cancer treatment. Spectrofluorometric, UV spectrophotometric, and fourier transform infrared (FT-IR) and molecular docking experiments were performed to study this interaction. The fluorescence of BSA is attributed to the presence of tryptophan (Trp) residues. The fluorescence of BSA in presence of neratinib was studied using the excitation wavelength of 280 nm and the emission was measured at 300-500 nm at three different temperatures. Neratinib quenched the BSA intrinsic fluorescence by static mechanism. A complex formation occurred due to the interaction leading to BSA absorption shift. The fluorescence, UV- absorption, three dimensional fluorescence and FT-IR data showed conformational changes occurred in BSA after interaction with neratinib. The binding constant values decreased as the temperature increased suggesting an instable complex formation at high temperature. Site I (sub-domain IIA) was observed as the principal binding site for neratinib. Hydrogen bonding and Van der Waals forces were suggested to be involved in the BSA-neratinib interaction due to the negative values of entropy and enthalpy changes.

Study of Interactions of an Anticancer Drug Neratinib With Bovine Serum Albumin: Spectroscopic and Molecular Docking Approach

Directory of Open Access Journals (Sweden)

Tanveer A. Wani

2018-03-01

Full Text Available Binding of therapeutic agents to plasma proteins, particularly to serum albumin, provides valuable information in the drug development. This study was designed to evaluate the binding interaction of neratinib with bovine serum albumin (BSA. Neratinib blocks HER2 signaling and is effective in trastuzumab-resistant breast cancer treatment. Spectrofluorometric, UV spectrophotometric, and fourier transform infrared (FT-IR and molecular docking experiments were performed to study this interaction. The fluorescence of BSA is attributed to the presence of tryptophan (Trp residues. The fluorescence of BSA in presence of neratinib was studied using the excitation wavelength of 280 nm and the emission was measured at 300-500 nm at three different temperatures. Neratinib quenched the BSA intrinsic fluorescence by static mechanism. A complex formation occurred due to the interaction leading to BSA absorption shift. The fluorescence, UV- absorption, three dimensional fluorescence and FT-IR data showed conformational changes occurred in BSA after interaction with neratinib. The binding constant values decreased as the temperature increased suggesting an instable complex formation at high temperature. Site I (sub-domain IIA was observed as the principal binding site for neratinib. Hydrogen bonding and Van der Waals forces were suggested to be involved in the BSA-neratinib interaction due to the negative values of entropy and enthalpy changes.

Molecular separation method and apparatus

International Nuclear Information System (INIS)

Villa-Aleman, E.

1996-01-01

A method and apparatus are disclosed for separating a gaseous mixture of chemically identical but physically different molecules based on their polarities. The gaseous mixture of molecules is introduced in discrete quantities into the proximal end of a porous glass molecular sieve. The molecular sieve is exposed to microwaves to excite the molecules to a higher energy state from a lower energy state, those having a higher dipole moment being excited more than those with a lower energy state. The temperature of the sieve kept cold by a flow of liquid nitrogen through a cooling jacket so that the heat generated by the molecules colliding with the material is transferred away from the material. The molecules thus alternate between a higher energy state and a lower one, with the portion of molecules having the higher dipole moment favored over the others. The former portion can then be extracted separately from the distal end of the molecular sieve. 2 figs

Distinct signalling properties of insulin receptor substrate (IRS)-1 and IRS-2 in mediating insulin/IGF-1 action

DEFF Research Database (Denmark)

Rabiee, Atefeh; Krüger, Marcus; Ardenkjær-Larsen, Jacob

2018-01-01

Insulin/IGF-1 action is driven by a complex and highly integrated signalling network. Loss-of-function studies indicate that the major insulin/IGF-1 receptor substrate (IRS) proteins, IRS-1 and IRS-2, mediate different biological functions in vitro and in vivo, suggesting specific signalling...... properties despite their high degree of homology. To identify mechanisms contributing to the differential signalling properties of IRS-1 and IRS-2 in the mediation of insulin/IGF-1 action, we performed comprehensive mass spectrometry (MS)-based phosphoproteomic profiling of brown preadipocytes from wild type......, IRS-1-/-and IRS-2-/-mice in the basal and IGF-1-stimulated states. We applied stable isotope labeling by amino acids in cell culture (SILAC) for the accurate quantitation of changes in protein phosphorylation. We found ~10% of the 6262 unique phosphorylation sites detected to be regulated by IGF-1...

Experimental and theoretical studies on IR, Raman, and UV-Vis spectra of quinoline-7-carboxaldehyde.

Science.gov (United States)

Kumru, M; Küçük, V; Kocademir, M; Alfanda, H M; Altun, A; Sarı, L

2015-01-05

Spectroscopic properties of quinoline-7-carboxaldehyde (Q7C) have been studied in detail both experimentally and theoretically. The FT-IR (4000-50 cm(-1)), FT-Raman (4000-50 cm(-1)), dispersive-Raman (3500-50 cm(-1)), and UV-Vis (200-400 nm) spectra of Q7C were recorded at room temperature (25 °C). Geometry parameters, potential energy surface about CCH(O) bond, harmonic vibrational frequencies, IR and Raman intensities, UV-Vis spectrum, and thermodynamic characteristics (at 298.15K) of Q7C were computed at Hartree-Fock (HF) and density functional B3LYP levels employing the 6-311++G(d,p) basis set. Frontier molecular orbitals, molecular electrostatic potential, and Mulliken charge analyses of Q7C have also been performed. Q7C has two stable conformers that are energetically very close to each other with slight preference to the conformer that has oxygen atom of the aldehyde away from the nitrogen atom of the quinoline. Copyright © 2014 Elsevier B.V. All rights reserved.

Second European study conference on molecular low energy collisions (MOLEC II)

Energy Technology Data Exchange (ETDEWEB)

1978-01-01

The conference contained 52 papers on molecular low energy collisions including nonadiabatic transitions and excited states, vibrational and rotational energy transfer, chemical reactions, dissociation and ionization, general methods, potential surfaces, electronic excitation and excited states, inelastic scattering and anisotropic potentials, chemical reactions, and Van der Waals molecules. (JFP)

Physiochemical Characteristics and Molecular Structures for Digestible Carbohydrates of Silages.

Science.gov (United States)

Refat, Basim; Prates, Luciana L; Khan, Nazir A; Lei, Yaogeng; Christensen, David A; McKinnon, John J; Yu, Peiqiang

2017-10-18

The main objectives of this study were (1) to assess the magnitude of differences among new barley silage varieties (BS) selected for varying rates of in vitro neutral detergent fiber (NDF) digestibility (ivNDFD; Cowboy BS with higher ivNDFD, Copeland BS with intermediate ivNDFD, and Xena BS with lower ivNDFD) with regard to their carbohydrate (CHO) molecular makeup, CHO chemical fractions, and rumen degradability in dairy cows in comparison with a new corn silage hybrid (Pioneer 7213R) and (2) to quantify the strength and pattern of association between the molecular structures and digestibility of carbohydrates. The carbohydrate-related molecular structure spectral data was measured using advanced vibrational molecular spectroscopy (FT/IR). In comparison to BS, corn silage showed a significantly (P carbohydrates were significantly (P carbohydrate content of the silages. In conclusion, the univariate approach with only one-factor consideration (ivNDFD) might not be a satisfactory method for evaluating and ranking BS quality. FT/IR molecular spectroscopy can be used to evaluate silage quality rapidly, particularly the digestible fiber content.

Laser excitation of SF6: spectroscopy and coherent pulse propagation effects

International Nuclear Information System (INIS)

Cantrell, C.D.; Makarov, A.A.; Louisell, W.H.

1978-01-01

Recent theoretical studies of coherent propagation effects in SF 6 and other polyatomic molecules are summarized beginning with an account of relevant aspects of the high-resolution spectroscopy of the ν 3 band of SF 6 . A laser pulse propagating in a molecular gas can acquire new frequencies which were not initially present in the pulse, and, in fact, a wave is coherently generated at the frequency of every molecular transition accessible from the initial molecular energy levels. The possible consequences of coherent generation of sidebands for the multiple-photon excitation of SF 6 and other polyatomic molecules are discussed

Vibrationally enhanced associative photodesorption of H{sub 2} (D{sub 2}) from Ru(0001). Quantum and classical approaches

Energy Technology Data Exchange (ETDEWEB)

Vazhappilly, Tijo Joseph

2008-04-15

This thesis investigates the femtosecond laser induced associative photodesorption of hydrogen, H{sub 2}, and deuterium, D{sub 2}, from a ruthenium metal surface. One of the goals of the present thesis is to suggest, on the basis of theoretical simulations, strategies to control/enhance the photodesorption yield from Ru(0001). For this purpose, we suggest a hybrid scheme to control the reaction, where the adsorbate vibrations are initially excited by an infrared (IR) pulse, prior to the vis pulse. Both adiabatic and non-adiabatic representations for photoinduced desorption problems are employed here. The adiabatic representation is realized within the classical picture using Molecular Dynamics (MD) with electronic frictions. In a quantum mechanical description, non-adiabatic representations are employed within open-system density matrix theory. The time evolution of the desorption process is studied using a two-mode reduced dimensionality model with one vibrational coordinate and one translational coordinate of the adsorbate. The ground and excited electronic state potentials, and dipole function for the IR excitation are taken from first principles. The IR driven vibrational excitation of adsorbate modes with moderate efficiency is achieved by (modified) {pi}-pulses or/and optimal control theory. The fluence dependence of the desorption reaction is computed by including the electronic temperature of the metal calculated from the two-temperature model. We then employed the IR+vis strategy in both models. Here, we found that vibrational excitation indeed promotes the desorption of hydrogen and deuterium. (orig.)

Distinct signalling properties of insulin receptor substrate (IRS)-1 and IRS-2 in mediating insulin/IGF-1 action.

Science.gov (United States)

Rabiee, Atefeh; Krüger, Marcus; Ardenkjær-Larsen, Jacob; Kahn, C Ronald; Emanuelli, Brice

2018-07-01

Insulin/IGF-1 action is driven by a complex and highly integrated signalling network. Loss-of-function studies indicate that the major insulin/IGF-1 receptor substrate (IRS) proteins, IRS-1 and IRS-2, mediate different biological functions in vitro and in vivo, suggesting specific signalling properties despite their high degree of homology. To identify mechanisms contributing to the differential signalling properties of IRS-1 and IRS-2 in the mediation of insulin/IGF-1 action, we performed comprehensive mass spectrometry (MS)-based phosphoproteomic profiling of brown preadipocytes from wild type, IRS-1 -/- and IRS-2 -/- mice in the basal and IGF-1-stimulated states. We applied stable isotope labeling by amino acids in cell culture (SILAC) for the accurate quantitation of changes in protein phosphorylation. We found ~10% of the 6262 unique phosphorylation sites detected to be regulated by IGF-1. These regulated sites included previously reported substrates of the insulin/IGF-1 signalling pathway, as well as novel substrates including Nuclear Factor I X and Semaphorin-4B. In silico prediction suggests the protein kinase B (PKB), protein kinase C (PKC), and cyclin-dependent kinase (CDK) as the main mediators of these phosphorylation events. Importantly, we found preferential phosphorylation patterns depending on the presence of either IRS-1 or IRS-2, which was associated with specific sets of kinases involved in signal transduction downstream of these substrates such as PDHK1, MAPK3, and PKD1 for IRS-1, and PIN1 and PKC beta for IRS-2. Overall, by generating a comprehensive phosphoproteomic profile from brown preadipocyte cells in response to IGF-1 stimulation, we reveal both common and distinct insulin/IGF-1 signalling events mediated by specific IRS proteins. Copyright © 2018 Elsevier Inc. All rights reserved.

Excitation two-center interference and the orbital geometry in laser-induced nonsequential double ionization of diatomic molecules

International Nuclear Information System (INIS)

Shaaran, T.; Augstein, B. B.; Figueira de Morisson Faria, C.

2011-01-01

We address the influence of the molecular orbital geometry and of the molecular alignment with respect to the laser-field polarization on laser-induced nonsequential double ionization of diatomic molecules for different molecular species, namely N 2 and Li 2 . We focus on the recollision excitation with subsequent tunneling ionization (RESI) mechanism, in which the first electron, upon return, promotes the second electron to an excited state, from where it subsequently tunnels. We assume that both electrons are initially in the highest occupied molecular orbital (HOMO) and that the second electron is excited to the lowest unoccupied molecular orbital (LUMO). We show that the electron-momentum distributions exhibit interference maxima and minima due to the electron emission at spatially separated centers. We provide generalized analytical expressions for such maxima or minima, which take into account s-p mixing and the orbital geometry. The patterns caused by the two-center interference are sharpest for vanishing alignment angle and get washed out as this parameter increases. Apart from that, there exist features due to the geometry of the LUMO, which may be observed for a wide range of alignment angles. Such features manifest themselves as the suppression of probability density in specific momentum regions due to the shape of the LUMO wave function, or as an overall decrease in the RESI yield due to the presence of nodal planes.

A WARM MOLECULAR HYDROGEN TAIL DUE TO RAM-PRESSURE STRIPPING OF A CLUSTER GALAXY

International Nuclear Information System (INIS)

Sivanandam, Suresh; Rieke, Marcia J.; Rieke, George H.

2010-01-01

We have discovered a remarkable warm (130-160 K) molecular hydrogen tail with a H 2 mass of approximately 4 x 10 7 M sun extending 20 kpc from a cluster spiral galaxy, ESO 137-001, in Abell 3627. At least half of this gas is lost permanently to the intracluster medium, as the tail extends beyond the tidal radius of the galaxy. We also detect a hot (400-550 K) component in the tail that is approximately 1% of the mass. The large H 2 line to IR continuum luminosity ratio in the tail indicates that star formation is not a major excitation source and that the gas is possibly shock-heated. This discovery confirms that the galaxy is currently undergoing ram-pressure stripping, as also indicated by its previously discovered X-ray and Hα tails. We estimate that the galaxy is losing its warm H 2 gas at a rate of ∼2-3 M sun yr -1 . The true mass-loss rate is likely higher if we account for cold molecular gas and atomic gas. We predict that the galaxy will lose most of its gas in a single pass through the core and place a strong upper limit on the ram-pressure timescale of 1 Gyr. We also study the star-forming properties of the galaxy and its tail. We identify most of the previously discovered external Hα sources within the tail in our 8 μm data but not in our 3.6 μm data; IRS spectroscopy of the region containing these Hα sources also reveals aromatic features typically associated with star formation. From the positions of these H II regions, it appears that star formation is not occurring throughout the molecular hydrogen tail but only immediately downstream of the galaxy. Some of these H II regions lie outside the tidal radius of the galaxy, indicating that ram-pressure stripping can be a source of intracluster stars.

Feeding of the 1 1/2- isomers in stable Ir and Au isotopes

Energy Technology Data Exchange (ETDEWEB)

Fotiadis, Nikolaos [Los Alamos National Laboratory; Nelson, Ronald O [Los Alamos National Laboratory; Devlin, Matthew [Los Alamos National Laboratory; Holloway, Shannon T [Los Alamos National Laboratory; Kawano, Toshihiko [Los Alamos National Laboratory; Talou, Patrick [Los Alamos National Laboratory; Chadwick, Mark B [Los Alamos National Laboratory; Becker, John A [LLNL; Garrett, Paul E [U GUELPH, CANADA

2008-01-01

Excited states were studied and absolute partial {gamma}-ray cross sections were measured using the ({eta}, {eta}'{gamma}) reaction in {sup 191}Ir, {sup 193}Ir and {sup 197}Au. A Compton-suppressed germanium-detector array (GEANIE) for {gamma}-ray spectroscopy and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's WNR facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Absolute partial {gamma}-ray cross sections were measured up to incident neutron energy of 20 MeV for several transitions feeding directly the 1 1/2- isomers and ground states in {sup 191}Ir, {sup 193}Ir and {sup 197}Au. The feeding of the 1 1/2- isomers, which originate from the odd proton occupying the h{sub 1 1/2} orbital, was found for the three targets to be very similar and increasing relative to the feeding of the corresponding ground state with increasing neutron energy up to E{sub n} {approx} 10 MeV. Above this neutron energy the opening of the (n, 2{sub n}) reaction channel strongly affects the population of the isomers and leads to a decrease of their relative population compared to the population of the ground states. The experimental results are compared with theoretical predictions from the GNASH reaction model calculation implementing a version of the spin distribution for the pre-equilibrium reaction piece with either a compound nucleus spin distribution (CN-GNASH) or a Feshbach-Kerman-Koonin (FKK-GNASH) quantum mechanical spin distribution. The effects of the spin cutoff parameter values on the population of states are examined. Evidence is presented that FKK-GNASH provides a description of the experimental data that mitigates the need for adjustment of the level density parameter to fit the data.

Harnessing molecular excited states with Lanczos chains

Science.gov (United States)

Baroni, Stefano; Gebauer, Ralph; Bariş Malcioğlu, O.; Saad, Yousef; Umari, Paolo; Xian, Jiawei

2010-02-01

The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.

Harnessing molecular excited states with Lanczos chains

Energy Technology Data Exchange (ETDEWEB)

Baroni, Stefano; Baris Malcioglu, O; Xian Jiawei [SISSA-Scuola Internazionale Superiore di Studi Avanzati, I-34151 Trieste (Italy); Gebauer, Ralph; Umari, Paolo [CNR DEMOCRITOS Theory-Elettra Group, c/o Sincrotrone Trieste, Area Science Park, I-34012 Basovizza, Trieste (Italy); Saad, Yousef [Department of Computer Science and Engineering, University of Minnesota, and Minnesota Supercomputing Institute, Minneapolis, MN 55455 (United States)

2010-02-24

The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.

Harnessing molecular excited states with Lanczos chains.

Science.gov (United States)

Baroni, Stefano; Gebauer, Ralph; Bariş Malcioğlu, O; Saad, Yousef; Umari, Paolo; Xian, Jiawei

2010-02-24

The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.

Harnessing molecular excited states with Lanczos chains

International Nuclear Information System (INIS)

Baroni, Stefano; Baris Malcioglu, O; Xian Jiawei; Gebauer, Ralph; Umari, Paolo; Saad, Yousef

2010-01-01

The recursion method of Haydock, Heine and Kelly is a powerful tool for calculating diagonal matrix elements of the resolvent of quantum-mechanical Hamiltonian operators by elegantly expressing them in terms of continued fractions. In this paper we extend the recursion method to off-diagonal matrix elements of general (possibly non-Hermitian) operators and apply it to the simulation of molecular optical absorption and photoemission spectra within time-dependent density-functional and many-body perturbation theories, respectively. This method is demonstrated with a couple of applications to the optical absorption and photoemission spectra of the caffeine molecule.

Anomalous High-Energy Waterfall-Like Electronic Structure in 5 d Transition Metal Oxide Sr2IrO4 with a Strong Spin-Orbit Coupling

Science.gov (United States)

Liu, Yan; Yu, Li; Jia, Xiaowen; Zhao, Jianzhou; Weng, Hongming; Peng, Yingying; Chen, Chaoyu; Xie, Zhuojin; Mou, Daixiang; He, Junfeng; Liu, Xu; Feng, Ya; Yi, Hemian; Zhao, Lin; Liu, Guodong; He, Shaolong; Dong, Xiaoli; Zhang, Jun; Xu, Zuyan; Chen, Chuangtian; Cao, Gang; Dai, Xi; Fang, Zhong; Zhou, X. J.

2015-08-01

The low energy electronic structure of Sr2IrO4 has been well studied and understood in terms of an effective Jeff = 1/2 Mott insulator model. However, little work has been done in studying its high energy electronic behaviors. Here we report a new observation of the anomalous high energy electronic structure in Sr2IrO4. By taking high-resolution angle-resolved photoemission measurements on Sr2IrO4 over a wide energy range, we have revealed for the first time that the high energy electronic structures show unusual nearly-vertical bands that extend over a large energy range. Such anomalous high energy behaviors resemble the high energy waterfall features observed in the cuprate superconductors. While strong electron correlation plays an important role in producing high energy waterfall features in the cuprate superconductors, the revelation of the high energy anomalies in Sr2IrO4, which exhibits strong spin-orbit coupling and a moderate electron correlation, points to an unknown and novel route in generating exotic electronic excitations.

Anomalous High-Energy Waterfall-Like Electronic Structure in 5 d Transition Metal Oxide Sr2IrO4 with a Strong Spin-Orbit Coupling.

Science.gov (United States)

Liu, Yan; Yu, Li; Jia, Xiaowen; Zhao, Jianzhou; Weng, Hongming; Peng, Yingying; Chen, Chaoyu; Xie, Zhuojin; Mou, Daixiang; He, Junfeng; Liu, Xu; Feng, Ya; Yi, Hemian; Zhao, Lin; Liu, Guodong; He, Shaolong; Dong, Xiaoli; Zhang, Jun; Xu, Zuyan; Chen, Chuangtian; Cao, Gang; Dai, Xi; Fang, Zhong; Zhou, X J

2015-08-12

The low energy electronic structure of Sr2IrO4 has been well studied and understood in terms of an effective Jeff = 1/2 Mott insulator model. However, little work has been done in studying its high energy electronic behaviors. Here we report a new observation of the anomalous high energy electronic structure in Sr2IrO4. By taking high-resolution angle-resolved photoemission measurements on Sr2IrO4 over a wide energy range, we have revealed for the first time that the high energy electronic structures show unusual nearly-vertical bands that extend over a large energy range. Such anomalous high energy behaviors resemble the high energy waterfall features observed in the cuprate superconductors. While strong electron correlation plays an important role in producing high energy waterfall features in the cuprate superconductors, the revelation of the high energy anomalies in Sr2IrO4, which exhibits strong spin-orbit coupling and a moderate electron correlation, points to an unknown and novel route in generating exotic electronic excitations.

Experimental system to measure excitation cross-sections by electron impact. Measurements for ArI and ArII

International Nuclear Information System (INIS)

Blanco, F.; Sanchez, J.A.; Aguilera, J.A.; Campos, J.

1989-01-01

An experimental set-up to measure excitation cross-section of atomic and molecular levels by electron impact based on the optical method is reported. We also present some measurements on the excitation cross-section for ArI 5p'(1/2)0 level, and for simultaneous ionization and excitation of Ar leading to ArII levels belonging to the 3p 4 4p and 3p 4 4d configurations. (Author)