Communication: Photodissociation of CH3CHO at 308 nm: Observation of H-roaming, CH3-roaming, and transition state pathways together along the ground state surface

Science.gov (United States)

Li, Hou-Kuan; Tsai, Po-Yu; Hung, Kai-Chan; Kasai, Toshio; Lin, King-Chuen

2015-01-01

Following photodissociation of acetaldehyde (CH3CHO) at 308 nm, the CO(v = 1-4) fragment is acquired using time-resolved Fourier-transform infrared emission spectroscopy. The CO(v = 1) rotational distribution shows a bimodal feature; the low- and high-J components result from H-roaming around CH3CO core and CH3-roaming around CHO radical, respectively, in consistency with a recent assignment by Kable and co-workers (Lee et al., Chem. Sci. 5, 4633 (2014)). The H-roaming pathway disappears at the CO(v ≥ 2) states, because of insufficient available energy following bond-breaking of H + CH3CO. By analyzing the CH4 emission spectrum, we obtained a bimodal vibrational distribution; the low-energy component is ascribed to the transition state (TS) pathway, consistent with prediction by quasiclassical trajectory calculations, while the high-energy component results from H- and CH3-roamings. A branching fraction of H-roaming/CH3-roaming/TS contribution is evaluated to be (8% ± 3%)/(68% ± 10%)/(25% ± 5%), in which the TS pathway was observed for the first time. The three pathways proceed concomitantly along the electronic ground state surface.

Photodissociation dynamics and spectroscopy of free radical combustion intermediates

Energy Technology Data Exchange (ETDEWEB)

Osborn, David Lewis [Univ. of California, Berkeley, CA (United States)

1996-12-01

The photodissociation spectroscopy and dynamics of free radicals is studied by the technique of fast beam photofragment translational spectroscopy. Photodetachment of internally cold, mass-selected negative ions produces a clean source of radicals, which are subsequently dissociated and detected. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states of the radical. In addition, the photodissociation dynamics, product branching ratios, and bond energies are probed at fixed photon energies by measuring the translational energy, P(E_T), and angular distribution of the recoiling fragments using a time- and position-sensitive detector. Ab initio calculations are combined with dynamical and statistical models to interpret the observed data. The photodissociation of three prototypical hydrocarbon combustion intermediates forms the core of this work.

Fast beam studies of free radical photodissociation

Energy Technology Data Exchange (ETDEWEB)

Neumark, D.M. [Lawrence Berkeley Laboratory, CA (United States)

1993-12-01

The authors have developed a novel technique for studying the photodissociation spectroscopy and dynamics of free radicals. In these experiments, radicals are generated by laser photodetachment of a fast (6-8 keV) mass-selected negative ion beam. The resulting radicals are photodissociated with a second laser, and the photofragments are collected and detected with high efficiency using a microchannel plate detector. The overall process is: ABC{sup -} {yields} ABC + e{sup -} {yields} A + BC, AB + C. Two types of fragment detection schemes are used. To map out the photodissociation cross-section of the radical, the photodissociation laser is scanned and the total photofragment yield is measured as a function of wavelength. In other experiments, the photodissociation frequency is fixed and the photofragment masses, kinetic energy release, and scattering angle is determined for each photodissociation event.

Discrete variable theory of triatomic photodissociation

International Nuclear Information System (INIS)

Heather, R.W.; Light, J.C.

1983-01-01

The coupled equations describing the photodissociation process are expressed in the discrete variable representation (DVR) in which the coupled equations are labeled by quadrature points rather than by internal basis functions. A large reduction in the dimensionality of the coupled equations can be realized since the spatially localized bound state nuclear wave function vanishes at most of the quadrature points, making only certain orientations of the fragments important in the region of strong interaction (small separation). The discrete variable theory of photodissociation is applied to the model dissociation of bent HCN in which the CN fragment is treated as a rigid rotor. The truncated DVR rotational distributions are compared with the exact close coupled rotational distributions, and excellent agreement with greatly reduced dimensionality of the equations is found

State-to-state photodissociation dynamics of triatomic molecules: H2O in the B band

International Nuclear Information System (INIS)

Jiang Bin; Xie Daiqian; Guo Hua

2012-01-01

State-to-state photodissociation dynamics of H 2 O in its B band has been investigated quantum mechanically on a new set of non-adiabatically coupled potential energy surfaces for the lowest two 1 A' states of H 2 O, which are developed at the internally contracted multi-reference configuration interaction level with the aug-cc-pVQZ basis set. Quantum dynamical calculations carried out using the Chebyshev propagator yield absorption spectra, product state distributions, branching ratios, and differential cross sections, which are in reasonably good agreement with the latest experimental results. Particular focus is placed here on the dependence of various dynamical observables on the photon energy. Detailed analyses of the dynamics have assigned the diffuse structure in absorption spectrum to short-time recurring dynamics near the HOH conical intersection. The non-adiabatic dissociation to the ground state OH product via the HOH conical intersection is facile, direct, fast, and produces rotationally hot OH(X-tilde) products. On the other hand, the adiabatic channel on the excited state leading to the OH(A-tilde) product is dominated by long-lived resonances, which depend sensitively on the potential energy surfaces.

Electronic and vibrational spectroscopy and vibrationally mediated photodissociation of V+(OCO).

Science.gov (United States)

Citir, Murat; Altinay, Gokhan; Metz, Ricardo B

2006-04-20

Electronic spectra of gas-phase V+(OCO) are measured in the near-infrared from 6050 to 7420 cm(-1) and in the visible from 15,500 to 16,560 cm(-1), using photofragment spectroscopy. The near-IR band is complex, with a 107 cm(-1) progression in the metal-ligand stretch. The visible band shows clearly resolved vibrational progressions in the metal-ligand stretch and rock, and in the OCO bend, as observed by Brucat and co-workers. A vibrational hot band gives the metal-ligand stretch frequency in the ground electronic state nu3'' = 210 cm(-1). The OCO antisymmetric stretch frequency in the ground electronic state (nu1'') is measured by using vibrationally mediated photodissociation. An IR laser vibrationally excites ions to nu1'' = 1. Vibrationally excited ions selectively dissociate following absorption of a second, visible photon at the nu1' = 1 CO2, due to interaction with the metal. Larger blue shifts observed for complexes with fewer ligands agree with trends seen for larger V+(OCO)n clusters.

Studies of combustion reactions at the state-resolved differential cross section level

Energy Technology Data Exchange (ETDEWEB)

Houston, P.L.; Suits, A.G.; Bontuyan, L.S.; Whitaker, B.J. [Cornell Univ., Ithaca, NY (United States)

1993-12-01

State-resolved differential reaction cross sections provide perhaps the most detailed information about the mechanism of a chemical reaction, but heretofore they have been extremely difficult to measure. This program explores a new technique for obtaining differential cross sections with product state resolution. The three-dimensional velocity distribution of state-selected reaction products is determined by ionizing the appropriate product, waiting for a delay while it recoils along the trajectory imparted by the reaction, and finally projecting the spatial distribution of ions onto a two dimensional screen using a pulsed electric field. Knowledge of the arrival time allows the ion position to be converted to a velocity, and the density of velocity projections can be inverted mathematically to provide the three-dimensional velocity distribution for the selected product. The main apparatus has been constructed and tested using photodissociations. The authors report here the first test results using crossed beams to investigate collisions between Ar and NO. Future research will both develop further the new technique and employ it to investigate methyl radical, formyl radical, and hydrogen atom reactions which are important in combustion processes. The authors intend specifically to characterize the reactions of CH{sub 3} with H{sub 2} and H{sub 2}CO; of HCO with O{sub 2}; and of H with CH{sub 4}, CO{sub 2}, and O{sub 2}.

Quantum treatment of the Ar-HI photodissociation dynamics

International Nuclear Information System (INIS)

Lopez-Lopez, Sergio; Prosmiti, Rita; Garcia-Vela, Alberto

2004-01-01

A wave packet simulation of the ultraviolet photolysis dynamics of Ar-HI(v=0) is reported. Cluster photodissociation is started from two different initial states, namely, the ground van der Waals (vdW) and the first excited vdW bending state, associated with the Ar-I-H and Ar-H-I isomeric forms of the system, respectively. Formation of Ar-I radical products is investigated over the energy range of the cluster absorption spectrum. It is found that the yield of bound Ar-I radical complexes is typically 90%-100% and 70%-80% for the initial states associated with the Ar-I-H and Ar-H-I isomers, respectively. This result is in agreement with the experimentally observed time-of-flight spectrum of the hydrogen fragment produced after Ar-HI photodissociation. The high Ar-I yield is explained mainly by the small amount of energy available for the radical that is converted into internal energy in the photofragmentation process, which enhances the Ar-I survival probability. Quantum interference effects manifest themselves in structures in the angular distribution of the hydrogen fragment, and in pronounced rainbow patterns in the rotational distributions of the Ar-I radical

Optimal laser control of ultrafast photodissociation of I2- in water: Mixed quantum/classical molecular dynamics simulation

International Nuclear Information System (INIS)

Nishiyama, Yoshikazu; Kato, Tsuyoshi; Ohtsuki, Yukiyoshi; Fujimura, Yuichi

2004-01-01

A linearized optimal control method in combination with mixed quantum/classical molecular dynamics simulation is used for numerically investigating the possibility of controlling photodissociation wave packets of I 2 - in water. Optimal pulses are designed using an ensemble of photodissociation samples, aiming at the creation of localized dissociation wave packets. Numerical results clearly show the effectiveness of the control although the control achievement is reduced with an increase in the internuclear distance associated with a target region. We introduce effective optimal pulses that are designed using a statistically averaged effective dissociation potential, and show that they semiquantitatively reproduce the control achievements calculated by using optimal pulses. The control mechanisms are interpreted from the time- and frequency-resolved spectra of the effective optimal pulses

Photodissociation dynamics of 2-chloro-6-nitrotoluene and nitrocyclopentane in gas phase: Laser-induced fluorescence detection of OH

Energy Technology Data Exchange (ETDEWEB)

Kawade, Monali N.; Saha, Ankur; Upadhyaya, Hari P.; Kumar, Awadhesh; Naik, Prakash D., E-mail: pdnaik@barc.gov.in

2014-10-31

Highlights: • Photodissociation studies on chloronitrotoluene (ClNT) and nitrocyclopentane (NCP). • Nascent OH product detected state selectively using laser induced fluorescence. • OH formation takes place from the ground electronic state with an exit barrier. • UV photodissociation dynamics of ClNT and NCP is different. - Abstract: Photodissociation of 2-chloro-6-nitrotoluene (ClNT) at 193, 248 and 266 nm and nitrocyclopentane (NCP) at 193 nm leads to the formation of OH, as detected by laser-induced fluorescence (LIF). The nascent OH produced from the photolysis of ClNT at all the wavelengths is vibrationally cold, with the Boltzmann type rotational state distributions. However, the nascent OH product from NCP is in the ground and vibrationally excited states with the measured average relative population in ν{sup ″}=1 to that in ν{sup ″}=0 of 0.12 ± 0.03, and these levels are characterized by rotational temperatures of 650 ± 180 K and 1570 ± 90 K, respectively. The translational energy partitioned in the OH fragment has been measured for photodissociation of both ClNT and NCP. On the basis of both the experimental results and the ground state molecular orbital (MO) calculations, a plausible mechanism for the OH formation has been proposed.

Photodissociation spectroscopy and dynamics of free radicals, clusters, and ions

Energy Technology Data Exchange (ETDEWEB)

Choi, Hyeon [Univ. of California, Berkeley, CA (United States)

1999-12-01

The photodissociation spectroscopy and dynamics of free radicals and ions is studied to characterize the dissociative electronic states in these species. To accomplish this, a special method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with the technique of fast beam photofragment translational spectroscopy. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states. Branching ratios to various product channels, the translational energy distributions of the fragments, and bond dissociation energies are then determined at selected photon energies. The detailed picture of photodissociation dynamics is provided with the aid of ab initio calculations and a statistical model to interpret the observed data. Important reaction intermediates in combustion reactions have been studied: CCO, C₂H₅O, and linear C_n (n = 4--6).

Femtosecond time-resolved photodissociation dynamics of methyl halide molecules on ultrathin gold films

Directory of Open Access Journals (Sweden)

Mihai E. Vaida

2011-09-01

Full Text Available The photodissociation of small organic molecules, namely methyl iodide, methyl bromide, and methyl chloride, adsorbed on a metal surface was investigated in real time by means of femtosecond-laser pump–probe mass spectrometry. A weakly interacting gold surface was employed as substrate because the intact adsorption of the methyl halide molecules was desired prior to photoexcitation. The gold surface was prepared as an ultrathin film on Mo(100. The molecular adsorption behavior was characterized by coverage dependent temperature programmed desorption spectroscopy. Submonolayer preparations were irradiated with UV light of 266 nm wavelength and the subsequently emerging methyl fragments were probed by photoionization and mass spectrometric detection. A strong dependence of the excitation mechanism and the light-induced dynamics on the type of molecule was observed. Possible photoexcitation mechanisms included direct photoexcitation to the dissociative A-band of the methyl halide molecules as well as the attachment of surface-emitted electrons with transient negative ion formation and subsequent molecular fragmentation. Both reaction pathways were energetically possible in the case of methyl iodide, yet, no methyl fragments were observed. As a likely explanation, the rapid quenching of the excited states prior to fragmentation is proposed. This quenching mechanism could be prevented by modification of the gold surface through pre-adsorption of iodine atoms. In contrast, the A-band of methyl bromide was not energetically directly accessible through 266 nm excitation. Nevertheless, the one-photon-induced dissociation was observed in the case of methyl bromide. This was interpreted as being due to a considerable energetic down-shift of the electronic A-band states of methyl bromide by about 1.5 eV through interaction with the gold substrate. Finally, for methyl chloride no photofragmentation could be detected at all.

Spin-State-Controlled Photodissociation of Iron(III) Azide to an Iron(V) Nitride Complex

Czech Academy of Sciences Publication Activity Database

Andris, E.; Navrátil, R.; Jašík, J.; Sabenya, G.; Costas, M.; Srnec, Martin; Roithová, J.

2017-01-01

Roč. 56, č. 45 (2017), s. 14057-14060 ISSN 1521-3773 Institutional support: RVO:61388955 Keywords : Ion spectroscopy * Iron(V) nitride * Photodissociation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

Photodissociation spectroscopy of the Mg+-acetic acid complex

Science.gov (United States)

Abate, Yohannes; Kleiber, P. D.

2006-11-01

We have studied the structure and photodissociation of Mg+-acetic acid clusters. Ab initio calculations suggest four relatively strongly bound ground state isomers for the [MgC2H4O2]+ complex. These isomers include the cis and trans forms of the Mg+-acetic acid association complex with Mg+ bonded to the carbonyl O atom of acetic acid, the Mg+-acetic acid association complex with Mg+ bonded to the hydroxyl O atom of acetic acid, or to a Mg+-ethenediol association complex. Photodissociation through the Mg+-based 3p←3s absorption bands in the near UV leads to direct (nonreactive) and reactive dissociation products: Mg+, MgOH+, Mg(H2O )+, CH3CO+, and MgCH3+. At low energies the dominant reactive quenching pathway is through dehydration to Mg(H2O)+, but additional reaction channels involving C-H and C-C bond activation are also open at higher energies.

Photodissociation and charge transfer dynamics of negative ions studied with femtosecond photoelectron spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Zanni, Martin Thomas [Univ. of California, Berkeley, CA (United States)

1999-12-01

This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents.

Photodissociation and charge transfer dynamics of negative ions studied with femtosecond photoelectron spectroscopy

International Nuclear Information System (INIS)

Zanni, Martin T.

1999-01-01

This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents

Photo-dissociation of hydrogen passivated dopants in gallium arsenide

International Nuclear Information System (INIS)

Tong, L.; Larsson, J.A.; Nolan, M.; Murtagh, M.; Greer, J.C.; Barbe, M.; Bailly, F.; Chevallier, J.; Silvestre, F.S.; Loridant-Bernard, D.; Constant, E.; Constant, F.M.

2002-01-01

A theoretical and experimental study of the photo-dissociation mechanisms of hydrogen passivated n- and p-type dopants in gallium arsenide is presented. The photo-induced dissociation of the Si Ga -H complex has been observed for relatively low photon energies (3.48 eV), whereas the photo-dissociation of C As -H is not observed for photon energies up to 5.58 eV. This fundamental difference in the photo-dissociation behavior between the two dopants is explained in terms of the localized excitation energies about the Si-H and C-H bonds

Photodissociation dynamics in the first absorption band of pyrrole. I. Molecular Hamiltonian and the Herzberg-Teller absorption spectrum for the A12(π σ* ) ←X˜ 1 A1(π π ) transition

Science.gov (United States)

Picconi, David; Grebenshchikov, Sergy Yu.

2018-03-01

This paper opens a series in which the photochemistry of the two lowest πσ* states of pyrrole and their interaction with each other and with the ground electronic state X ˜ are studied using ab initio quantum mechanics. New 24-dimensional potential energy surfaces for the photodissociation of the N-H bond and the formation of the pyrrolyl radical are calculated using the multiconfigurational perturbation theory (CASPT2) for the electronic states X ˜ (π π ) , 11A2(πσ*), and 11B1(πσ*) and locally diabatized. In this paper, the ab initio calculations are described and the photodissociation in the state 11A2(πσ*) is analyzed. The excitation 11 A2←X ˜ is mediated by the coordinate dependent transition dipole moment functions constructed using the Herzberg-Teller expansion. Nuclear dynamics, including 6, 11, and 15 active degrees of freedom, are studied using the multi-configurational time-dependent Hartree method. The focus is on the frequency resolved absorption spectrum as well as on the dissociation time scales and the resonance lifetimes. Calculations are compared with available experimental data. An approximate convolution method is developed and validated, with which absorption spectra can be calculated and assigned in terms of vibrational quantum numbers. The method represents the total absorption spectrum as a convolution of the diffuse spectrum of the detaching H-atom and the Franck-Condon spectrum of the heteroaromatic ring. Convolution calculation requires a minimal quantum chemical input and is a promising tool for studying the πσ* photodissociation in model biochromophores.

Near ultraviolet photodissociation spectroscopy of Mn{sup +}(H{sub 2}O) and Mn{sup +}(D{sub 2}O)

Energy Technology Data Exchange (ETDEWEB)

Pearson, Wright L.; Copeland, Christopher; Kocak, Abdulkadir; Sallese, Zachary; Metz, Ricardo B., E-mail: rbmetz@chem.umass.edu [Department of Chemistry, University of Massachusetts Amherst, Amherst, Massachusetts 01003 (United States)

2014-11-28

The electronic spectra of Mn{sup +}(H{sub 2}O) and Mn{sup +}(D{sub 2}O) have been measured from 30 000 to 35 000 cm{sup −1} using photodissociation spectroscopy. Transitions are observed from the {sup 7}A{sub 1} ground state in which the Mn{sup +} is in a 3d{sup 5}4s{sup 1} electronic configuration, to the {sup 7}B{sub 2} (3d{sup 5}4p{sub y}) and {sup 7}B{sub 1} (3d{sup 5}4p{sub x}) excited states with T{sub 0} = 30 210 and 32 274 cm{sup −1}, respectively. Each electronic transition has partially resolved rotational and extensive vibrational structure with an extended progression in the metal−ligand stretch at a frequency of ∼450 cm{sup −1}. There are also progressions in the in-plane bend in the {sup 7}B{sub 2} state, due to vibronic coupling, and the out-of-plane bend in the {sup 7}B{sub 1} state, where the calculation illustrates that this state is slightly non-planar. Electronic structure computations at the CCSD(T)/aug-cc-pVTZ and TD-DFT B3LYP/6-311++G(3df,3pd) level are also used to characterize the ground and excited states, respectively. These calculations predict a ground state Mn-O bond length of 2.18 Å. Analysis of the experimentally observed vibrational intensities reveals that this bond length decreases by 0.15 ± 0.015 Å and 0.14 ± 0.01 Å in the excited states. The behavior is accounted for by the less repulsive p{sub x} and p{sub y} orbitals causing the Mn{sup +} to interact more strongly with water in the excited states than the ground state. The result is a decrease in the Mn-O bond length, along with an increase in the H-O-H angle. The spectra have well resolved K rotational structure. Fitting this structure gives spin-rotation constants ε{sub aa}″ = −3 ± 1 cm{sup −1} for the ground state and ε{sub aa}′ = 0.5 ± 0.5 cm{sup −1} and ε{sub aa}′ = −4.2 ± 0.7 cm{sup −1} for the first and second excited states, respectively, and A′ = 12.8 ± 0.7 cm{sup −1} for the first excited state. Vibrationally mediated

Photodissociation of HBr/LiF(001) - A quantum mechanical model

Science.gov (United States)

Seideman, Tamar

1993-01-01

The photodissociation dynamics of HBr adsorbed on an LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation line shape and the Br(2P(1/2))/Br(2P(3/2)) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. We find the field polarization to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

Photodissociation of HBr/LiF(001): A quantum mechanical model

Science.gov (United States)

Seideman, Tamar

1993-01-01

The photodissociation dynamics of HBr adsorbed on a LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation lineshape and the Br(P(sub 1/2)-2)/Br(P(sub 3/2)-2) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. The field polarization is found to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase.

Photodissociation dynamics of 1-propanol and 2-propanol at 193.3 nm

International Nuclear Information System (INIS)

Zhou Weidong; Yuan Yan; Zhang Jingsong

2003-01-01

193.3-nm photodissociation dynamics of jet-cooled 1-propanol and 2-propanol and their partially deuterated variants are examined by using the high-n Rydberg-atom time-of-flight technique. Isotope labeling studies show that O-H bond fission is the primary H-atom production channel in the ultraviolet photodissociation of both 1-propanol and 2-propanol. Center-of-mass (c.m.) product translational energy release of the RO-H dissociation channel is large, with T >=0.78 for H+1-propoxy (n-propoxy) and 0.79 for H+2-propoxy (isoproxy). Maximum c.m. translational energy release yields an upper limit of the O-H bond dissociation energy: 433±2 kJ/mol in 1-propanol and 435±2 kJ/mol in 2-propanol. H-atom product angular distribution is anisotropic (with β≅-0.79 for 1-propanol and -0.77 for 2-propanol), suggesting an electronic transition moment perpendicular to the H-O-C plane and a short excited-state dissociation lifetime (less than a rotational period). Information about photodissociation dynamics and bond energies of the partially deuterated propanols are also obtained. The 193.3-nm photodissociation dynamics of 1-propanol and 2-propanol are nearly identical to each other and are similar to those of methanol and ethanol. This indicates a common RO-H dissociation mechanism: after the n O →σ * (O-H)/3s excitation localized on the H-O-C moiety, the H atom is ejected promptly in the H-O-C plane in a time scale shorter than a rotational period of the parent molecule, and it dissociates along the O-H coordinate on the repulsive excited-state potential-energy surface with a large translational energy release

Photodissociation of OCS: deviations between theory and experiment, and the importance of higher order correlation effects.

Science.gov (United States)

Schmidt, J A; Olsen, J M H

2014-11-14

The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 2(1)A' (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 1(1)A″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO.

Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects

International Nuclear Information System (INIS)

Schmidt, J. A.; Olsen, J. M. H.

2014-01-01

The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 2 1 A ′ (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 1 1 A ″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO

The Photodissociation of HCN and HNC: Effects on the HNC/HCN Abundance Ratio in the Interstellar Medium

Energy Technology Data Exchange (ETDEWEB)

Aguado, Alfredo [Departamento de Química Física Aplicada (UAM), Unidad Asociada a IFF-CSIC, Facultad de Ciencias Módulo 14, Universidad Autónoma de Madrid, E-28049, Madrid (Spain); Roncero, Octavio; Zanchet, Alexandre [Instituto de Física Fundamental (IFF-CSIC), C.S.I.C., Serrano 123, E-28006 Madrid (Spain); Agúndez, Marcelino; Cernicharo, José, E-mail: octavio.roncero@csic.es [Instituto de Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz 3, Cantoblanco E-28049 (Spain)

2017-03-20

The impact of the photodissociation of HCN and HNC isomers is analyzed in different astrophysical environments. For this purpose, the individual photodissociation cross sections of HCN and HNC isomers have been calculated in the 7–13.6 eV photon energy range for a temperature of 10 K. These calculations are based on the ab initio calculation of three-dimensional adiabatic potential energy surfaces of the 21 lower electronic states. The cross sections are then obtained using a quantum wave packet calculation of the rotational transitions needed to simulate a rotational temperature of 10 K. The cross section calculated for HCN shows significant differences with respect to the experimental one, and this is attributed to the need to consider non-adiabatic transitions. Ratios between the photodissociation rates of HCN and HNC under different ultraviolet radiation fields have been computed by renormalizing the rates to the experimental value. It is found that HNC is photodissociated faster than HCN by a factor of 2.2 for the local interstellar radiation field and 9.2 for the solar radiation field, at 1 au. We conclude that to properly describe the HNC/HCN abundance ratio in astronomical environments illuminated by an intense ultraviolet radiation field, it is necessary to use different photodissociation rates for each of the two isomers, which are obtained by integrating the product of the photodissociation cross sections and ultraviolet radiation field over the relevant wavelength range.

Ultraviolet photodissociation dynamics of the benzyl radical.

Science.gov (United States)

Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong

2011-05-14

Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy, , is ∼0.3. The P(E(T))s indicate the production of fulvenallene + H, which was suggested by recent theoretical studies. The H-atom product angular distribution is isotropic, with the anisotropy parameter β ≈ 0. The H/D product ratios from isotope labeling studies using C(6)H(5)CD(2) and C(6)D(5)CH(2) are reasonably close to the statistical H/D ratios, suggesting that the H/D atoms are scrambled in the photodissociation of benzyl. The dissociation mechanism is consistent with internal conversion of the electronically excited benzyl followed by unimolecular decomposition of the hot benzyl radical on the ground state.

Iron monoxide photodissociation

Science.gov (United States)

Chestakov, D. A.; Parker, D. H.; Baklanov, A. V.

2005-02-01

The photodissociation of Fe56O was studied by means of the velocity map imaging technique. A molecular beam of iron atoms and iron monoxide molecules was created using an electrical discharge with an iron electrode in a supersonic expansion of molecular oxygen. The ground state iron atom Fe(D45) and FeO concentrations in the molecular beam have been estimated. The dissociation energy of the FeO XΔ5 ground electronic state was found to be D00(FeO )=4.18±0.01eV. The effective absorption cross section of FeO at 252.39nm (vac), leading to the Fe(D45)+O(P3) dissociation channel, is ˜1.2×10-18cm2. A (1+1) resonantly enhanced multiphoton ionization spectrum of Fe56O in the region 39550-39580 cm-1 with rotational structure has been observed, but not assigned. Angular distributions of Fe(D45) and Fe(D35) products for the channel FeO →Fe(D4,35)+O(P3) have been measured at several points in the 210-260nm laser light wavelength region. The anisotropy parameter varies strongly with wavelength for both channels.

Photodissociation of dibromoethanes at 248 nm: an ignored channel of Br2 elimination.

Science.gov (United States)

Lee, Hsin-Lung; Lee, Ping-Chen; Tsai, Po-Yu; Lin, King-Chuen; Kuo, H H; Chen, P H; Chang, A H H

2009-05-14

Br(2) molecular elimination is probed in the photodissociation of 1,1- and 1,2-C(2)H(4)Br(2) isomeric forms at 248 nm by using cavity ring-down absorption spectroscopy. Their photodissociation processes differ markedly from each other. The quantum yield of the Br(2) fragment in 1,2-dibromoethane is 0.36+/-0.18, in contrast to a value of 0.05+/-0.03 in 1,1-dibromoethane. The vibrational population ratios of Br(2)(v=1)/Br(2)(v=0) are 0.8+/-0.1 and 0.5+/-0.2 for 1,2- and 1,1-dibromoethanes, respectively. The Br(2) yield densities are found to increase by a factor of 35% and 190% for 1,2- and 1,1-dibromoethanes within the same temperature increment. In the ab initio potential energy calculations, the transition state (TS) along the adiabatic ground state surface may correlate to the Br(2) products. The TS energy for 1,2-dibromoethane is well below the excitation energy at 483 kJ/mol, whereas that for 1,1-dibromoethane is slightly above. Such a small TS energy barrier impedes the photodissociation of the ground state 1,1-dibromoethane such that the production yield of Br(2) may become relatively low, but rise rapidly with the temperature. The TS structure shows a larger bond distance of Br-Br in 1,2-dibromoethane than that in 1,1-dibromoethane. That explains why the former isomer may result in hotter vibrational population of the Br(2) fragments.

Iodine photodissociation laser SOFIA with MOPO-HF as a solid-state oscillator

Czech Academy of Sciences Publication Activity Database

Dostál, Jan; Turčičová, Hana; Králiková, Božena; Král, Lukáš; Huynh, J.

2009-01-01

Roč. 97, č. 3 (2009), 687-694 ISSN 0946-2171 R&D Projects: GA ČR GA202/06/0814; GA MŠk(CZ) LC528; GA MŠk LN00A100 Grant - others:EC - 6FP LASERLAB-EUROPE(XE) RII3-CT-2003-506350 Program:FP6 Institutional research plan: CEZ:AV0Z10100523 Keywords : Iodine photodissociation laser * optical parametric amplification * chirped pulse * optical synchronization * stabilization of wavelength and pointing Subject RIV: BH - Optics, Masers, Lasers Impact factor: 1.992, year: 2009

Vacuum ultraviolet photoionization and photodissociation of polyatomic molecules and radicals

Energy Technology Data Exchange (ETDEWEB)

Ng, C.Y. [Iowa State Univ., Ames (United States)

1993-12-01

In the past decade, tremendous progress has been made in understanding the photodissociation (PD) dynamics of triatomic molecules. However, the PD study of radicals, especially polyatomic radicals, has remained essentially an unexplored research area. Detailed state-to-state PD cross sections for radicals in the UV and VUV provide challenges not only for dynamical calculations, but also for ab initio quantum chemical studies. The authors have developed a laser based pump-probe apparatus for the measurement of absolute PD cross sections for CH{sub 3}S and HS is summarized.

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

Intracluster superelastic scattering via sequential photodissociation in small HI clusters

International Nuclear Information System (INIS)

Chastaing, D.; Underwood, J.; Wittig, C.

2003-01-01

The photodissociation of expansion-cooled HI monomer by using 266 nm radiation yields H atoms having 12 830 and 5287 cm-1 of translational energy in the HI center-of-mass system for the I( 2 P 3/2 ) and I( 2 P 1/2 ) (i.e., I and I * , respectively) co-fragments. Irradiating HI clusters [i.e., (HI) n , with n=2 being the dominant cluster] with 266 nm radiation produces, among other things, some H atoms whose translational energies are peaked at 20 285 cm-1, which is 7455 cm-1 higher in energy than the more energetic of the monomer peaks. These very fast H atoms arise from sequential photodissociation within the clusters. Namely, a weakly bound I*·(HI) n-1 complex is first created by the photodissociation of an HI moiety within (HI) n , and then the photodissociation of a second HI moiety [within I*·(HI) n-1 ] produces a fast H atom that scatters from the nearby I*, in some cases deactivating it in the process. Thus, the latter superelastically scattered H atom acquires, as translational energy, nearly all of the I* energy (7603 cm-1). For example, for the dimer, the first dissociation event, (HI) 2 +hv→H+I(I*)·HI, is followed by I*·HI+hv→H superelastic +I-I. High quality potentials for the relevant HI excited states have been calculated recently, and coupling between 3 Π 0 + (which correlates with I * ) and 1 Π (which correlates with I) has been shown to be due to spin-rotation interaction. There is a high degree of separability between the photodissociation of the second HI moiety and the subsequent H+I * scattering (within a given cluster). This is due mainly to the shape of the 3 Π 0 + potential; specifically, it has a shallow well that persists to small r. The shape of the 3 Π 0 + potential is influenced by relativity; i.e., strong spin-orbit coupling maintains the I* spherical electron density to relatively small r. The 3 Π 0 + → 1 Π transition probabilities are calculated for H+I * collisions having different values of the collisional orbital

Multiphonon generation during photodissociation of slow Landau-Pekar polarons

International Nuclear Information System (INIS)

Myasnikov, E. N.; Myasnikova, A. E.; Mastropas, Z. P.

2006-01-01

The spectra of the low-temperature photodissociation (photoionization) of Landau-Pekar polarons are calculated using the theory of quantum-coherent states and a new method of variation with respect to the parameters of phonon vacuum deformation. It is shown that the final polaron states upon photodissociation may have different numbers of phonons produced in a single dissociation event and different momenta of charge carriers. The spectrum of optical absorption related to the photodissociation of polarons exhibits a superposition of bands corresponding to various numbers of phonons formed as a result of dissociation of a single polaron. Due to a large width of the energy region corresponding to the final states of charge carriers, the halfwidth of each band is on the order of the energy of polaron coupling and is much greater than the phonon energy. For this reason, the individual phonon bands exhibit strong overlap. The very broad and, probably, structureless band formed as a result of the superposition of all these components begins at an energy equal to the sum of the polaron coupling energy (E p ) and the phonon energy. This band has a maximum at a frequency of about 5.6E p /ℎ and a halfwidth on the order of 5.6E p /ℎ at a unit effective mass (m* = m e ) of band electrons. For an effective charge carrier mass within m* = (1-3)m e , the energy of the polaron band maximum can be estimated as 5E p with an error of about 10%, and the halfwidth falls within 3.4E p 1/2 p . The multiphonon character of this band is related to a decay of the phonon condensate after the escape of charge carrier from a polaron. Such polarons are likely to be observed in the spectra of complex metal oxides, including high-temperature superconductors. Examples of such polaron bands in the reported absorption and photoconductivity spectra of nonstoichiometric cuprates, manganites, nickelates, and titanates are presented. A theory of the formation of Landau-Pekar polarons with the

The photodissociation and reaction dynamics of vibrationally excited molecules

Energy Technology Data Exchange (ETDEWEB)

Crim, F.F. [Univ. of Wisconsin, Madison (United States)

1993-12-01

This research determines the nature of highly vibrationally excited molecules, their unimolecular reactions, and their photodissociation dynamics. The goal is to characterize vibrationally excited molecules and to exploit that understanding to discover and control their chemical pathways. Most recently the author has used a combination of vibrational overtone excitation and laser induced fluorescence both to characterize vibrationally excited molecules and to study their photodissociation dynamics. The author has also begun laser induced grating spectroscopy experiments designed to obtain the electronic absorption spectra of highly vibrationally excited molecules.

Formation and femtosecond photodissociation of Agn+andAun+ complexes with benzene and carbon monoxide

Science.gov (United States)

Popolan, Denisia M.; Bernhardt, Thorsten M.

2009-02-01

The reactions of free, size selected gold and silver cluster cations Agn+andAun+ ( n = 3, 5) with C 6H 6 as well as with a mixture of C 6H 6 and CO were investigated in a radio frequency ion trap under multiple collision condition. While benzene was found to react with all investigated metal clusters exhibiting size dependent adsorbate coverages, the coadsorption of C 6H 6 and CO was only observed on the gold clusters. Photodissociation experiments at 353 and 393 nm, respectively, provided indications for charge transfer induced fragmentation in the case of the silver cluster-benzene complexes. In particular, for Ag(CH)2+ the femtosecond time resolved fragmentation dynamics could be measured.

Theoretical treatment of photodissociation of water by time-dependent quantum mechanical methods

International Nuclear Information System (INIS)

Weide, K.

1993-01-01

An algorithm for wavepacket propagation, based on Kosloff's method of expansion of the time evolution operator in terms of Chebychev polynomials, and some details of its implementation are described. With the programs developed, quantum-mechanical calculations for up to three independent molecular coordinates are possible and feasible and therefore photodissociation of non-rotating triatomic molecules can be treated exactly. The angular degree of freedom here is handled by expansion in terms of free diatomic rotor states. The time-dependent wave packet picture is compared with the more traditional view of stationary wave functions, and both are used to interpret computational results where appropriate. Two-dimensional calculations have been performed to explain several experimental observations about water photodissociation. All calculations are based on ab initio potential energy surfaces, and it is explained in each case why it is reasonable to neglect the third degree of freedom. Many experimental results are reproduced quantitatively. (orig.) [de

DC slice ion imaging study of atomic orbital orientation and alignment in photodissociation

Science.gov (United States)

Lee, Suk Kyoung

A complete study of atomic photofragment polarization has been achieved by using DC slice imaging, a recently developed approach directly providing the central slice of the full 3D product distribution without any mathematical transformation. In this dissertation, the quantum mechanical treatment adapted for the sliced images has been derived to extract the angular momentum polarization anisotropy parameters for any recoil speeds. The important photodissociation dynamics of small polyatomic molecules has been presented based on the thorough interpretation of the observed orientation and alignment. The first demonstration of DC slice imaging of orbital polarization was a study of the 193 nm photodissociation of ethylene sulfide, followed by detailed investigation in ozone and OCS. In ozone, the speed-dependent orientation was measured for O(1D2) atom produced from photodissociation in the 248--285 nm region. The results show negligible orbital orientation following dissociation by circularly polarized light but strong recoil speed-dependent orientation following photolysis by linearly polarized light at all wavelengths studied. The origin of this polarization is ascribed to nonadiabatic transitions at avoided crossings and at long range. The atomic orbital alignment and orientation, including the higher order moments (K = 3, 4), has been carried out for the photodissociation of OCS at 193 nm. The observed speed-dependent beta and polarization parameters of S(1D2) atom support the interpretation that there are two main dissociation processes: a simultaneous two-surface excitation and the initial single-surface excitation followed by the nonadiabatic crossing to the ground state. The angle- and speed-dependent density matrix can be constructed containing the higher order contributions for circularly-polarized dissociation light. It was shown in one case that the higher order contributions should not be overlooked for an accurate picture of the dissociation dynamics in

High power atomic iodine photodissociation lasers

International Nuclear Information System (INIS)

Palmer, R.E.; Padrick, T.D.; Jones, E.D.

1976-01-01

The atomic iodine photodissociation laser has developed into a system capable of producing nanosecond or shorter pulses of near infrared radiation with energies well in excess of a hundred J. Discussed are the operating characteristics, advantages, and potential problem areas associated with this laser

Photodissociation of Small Molecules and Photoionization of Free Radicals Using the VUV Velocity-Map Imaging Photoion and Photoelectron Method

Science.gov (United States)

Gao, Hong

The tunable vacuum ultraviolet (VUV) laser generated through the two-photon resonance-enhanced four-wave mixing scheme is combined with the newly developed time-slice velocity map imaging photoion method to study the photodissociation of small molecules in the VUV region, and with the velocity map imaging photoelectron method to study the photoionization of free radicals. The photodissociation dynamics of NO in the energy region around 13.5 eV has been investigated. Branching ratios of the three lowest dissociation channels of 12C 16O that produce C(3P) + O(3P), C( 1D) + O(3P) and C(3P) + O(1D) are measured for the first time in the VUV region from 102,500 cm-1 to 110,500 cm-1, valuable information of the dissociation dynamics for this prototype system has been deduced. We demonstrated an experiment that has two independently tunable VUV lasers and a time-slice velocity map imaging setup, this provides us a global way to perform systematic state-selected photodissociation of small molecules via state-selected detection of the atomic products in the VUV region. The velocity map imaging photoelectron method was successfully used to obtain the photoelectron spectrum of the propargyl radical (C3H3) via a single VUV photoionization process. The propargyl radical is generated by the 193 nm laser photodissociation of the precursor C3H3Cl. This is the first time that the velocity map imaging photoelectron method is used to get the photoelectron spectra of free radicals, indicating that it is a powerful technique for studying the photoionization of free radicals which are always hard to be produced with high enough number densities for spectroscopic studies. This dissertation is mainly based on the following peer-reviewed journal articles: 1. Hong Gao, Yang Pan, Lei Yang, Jingang Zhou, C. Y. Ng and William M. Jackson. "Time-slice velocity-map ion imaging studies of the Photodissociation of NO in the vacuum ultraviolet region", the Journal of Chemical Physics, 136, 134302

Photodissociation dynamics of 2-chloro-6-nitrotoluene and nitrocyclopentane in gas phase: Laser-induced fluorescence detection of OH

Science.gov (United States)

Kawade, Monali N.; Saha, Ankur; Upadhyaya, Hari P.; Kumar, Awadhesh; Naik, Prakash D.

2014-10-01

Photodissociation of 2-chloro-6-nitrotoluene (ClNT) at 193, 248 and 266 nm and nitrocyclopentane (NCP) at 193 nm leads to the formation of OH, as detected by laser-induced fluorescence (LIF). The nascent OH produced from the photolysis of ClNT at all the wavelengths is vibrationally cold, with the Boltzmann type rotational state distributions. However, the nascent OH product from NCP is in the ground and vibrationally excited states with the measured average relative population in ν″ = 1 to that in ν″ = 0 of 0.12 ± 0.03, and these levels are characterized by rotational temperatures of 650 ± 180 K and 1570 ± 90 K, respectively. The translational energy partitioned in the OH fragment has been measured for photodissociation of both ClNT and NCP. On the basis of both the experimental results and the ground state molecular orbital (MO) calculations, a plausible mechanism for the OH formation has been proposed.

Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state

Science.gov (United States)

Xie, Changjian; Guo, Hua

2018-01-01

The choice of the active degrees of freedom (DOFs) is a pivotal issue in a reduced-dimensional model of quantum dynamics when a full-dimensional one is not feasible. Here, several five-dimensional (5D) models are used to investigate the nonadiabatic photodissociation dynamics of the hydroxymethyl (CH2OH) radical, which possesses nine internal DOFs, in its lowest absorption band. A normal-mode based scheme is used to identify the active and spectator modes, and its predictions are confirmed by 5D quantum dynamical calculations. Our results underscore the important role of the CO stretching mode in the photodissociation dynamics of CH2OH, originating from the photo-induced promotion of an electron from the half-occupied π*CO antibonding orbital to a carbon Rydberg orbital.

Isotope effects in photodissociation: Chemical reaction dynamics and implications for atmospheres

DEFF Research Database (Denmark)

Jørgensen, Solvejg; Grage, Mette Marie-Louise; Nyman, Gunnar

2008-01-01

obtaining the absorption and/or photodissociation cross section is a threefold challenge: computing the electronic potential energy surfaces, interpolating the potentials, and finding the cross section either by time-dependent or time-independent methods. We review electronic structure methods used...... for computing accurate potential energy surfaces for the electronic ground and accessible excited state as well as coupling between them (electronic transition dipole moments and diabatic coupling). Methods used for interpolation are discussed. The time-independent methods are based on the reflection principle...

Theoretical study of ultraviolet induced photodissociation dynamics of sulfuric acid

Energy Technology Data Exchange (ETDEWEB)

Murakami, Tatsuhiro; Ohta, Ayumi; Suzuki, Tomoya; Ikeda, Kumiko [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Danielache, Sebastian O. [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Earth-Life Science Institute (ELSI), Tokyo Institute of Technology (Japan); Department of Environmental Science and Techonology, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yoohama 226-8502 (Japan); Nanbu, Shinkoh, E-mail: shinkoh.nanbu@sophia.ac.jp [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan)

2015-05-01

Highlights: • Photodissociation dynamics of H{sub 2}SO{sub 4} at low-lying electronically excited states were investigated. • Photochemical processes were simulated by on-the-fly ab initio MD. • Sulfuric acid after the excitation to the S{sub 1} state dissociated to HSO{sub 4}(1{sup 2}A″) + H({sup 2}S). • Sulfuric acid after the excitation to the S{sub 2} state dissociated to HSO{sub 4}(2{sup 2}A″) + H({sup 2}S). • The energy region of the UV spectra where NMD fractionation may occur is predicted. - Abstract: Photodissociation dynamics of sulfuric acid after excitation to the first and second excited states (S{sub 1} and S{sub 2}) were studied by an on-the-fly ab initio molecular dynamics simulations based on the Zhu–Nakamura version of the trajectory surface hopping (ZN-TSH). Forces acting on the nuclear motion were computed on-the-fly by CASSCF method with Dunning’s augmented cc-pVDZ basis set. It was newly found that the parent molecule dissociated into two reaction-channels (i) HSO{sub 4}(1{sup 2}A″) + H({sup 2}S) by S{sub 1}-excitation, and (ii) HSO{sub 4}(2{sup 2}A″) + H({sup 2}S) by S{sub 2}-excitation. The direct dissociation dynamics yield products different from the SO{sub 2} + 2OH fragments often presented in the literature. Both channels result in the same product and differs only in the electronic state of the HSO{sub 4} fragment{sub .} The trajectories running on S{sub 2} do not hop with S{sub 0} and a nonadiabatic transition happens at the S{sub 2}–S{sub 1} conical intersection located at a longer OH bond-length than the S{sub 1}–S{sub 0} intersection producing an electronic excited state (2{sup 2}A″) of HSO{sub 4} product.

Photodissociation of hydrogen iodide on the surface of large argon clusters: The orientation of the librational wave function and the scattering from the cluster cage

International Nuclear Information System (INIS)

Slavicek, Petr; Jungwirth, Pavel; Lewerenz, Marius; Nahler, N. Hendrik; Farnik, Michal; Buck, Udo

2004-01-01

A set of photodissociation experiments and simulations of hydrogen iodide (HI) on Ar n clusters, with an average size =139, has been carried out for different laser polarizations. The doped clusters are prepared by a pick-up process. The HI molecule is then photodissociated by a UV laser pulse and the outgoing H fragment is ionized by resonance enhanced multiphoton ionization in a (2+1) excitation scheme within the same laser pulse at the wavelength of 243 nm. The measured time-of-flight spectra are transformed into hydrogen kinetic energy distributions. They exhibit a strong fraction of caged H atoms at zero-kinetic energy and peaks at the unperturbed cage exit for both spin-orbit channels nearly independent of the polarization. At this dissociation wavelength, the bare HI molecule exhibits a strict state separation, with a parallel transition to the spin-orbit excited state and perpendicular transitions to the ground state. The experimental results have been reproduced using molecular simulation techniques. Classical molecular dynamics was used to estimate the HI dopant distribution after the pick-up procedure. Subsequently, quasi-classical molecular dynamics (Wigner trajectories approach) has been applied for the photodissociation dynamics. The following main results have been obtained: (i) The HI dopant lands on the surface of the argon cluster during the pick-up process, (ii) zero-point energy plays a dominant role for the hydrogen orientation in the ground state of HI-Ar n surface clusters, qualitatively changing the result of the photodissociation experiment upon increasing the number of argon atoms, and, finally, (iii) the scattering of hydrogen atoms from the cage which originate from different dissociation states seriously affects the experimentally measured kinetic energy distributions

Photodissociation dynamics of the methyl perthiyl radical at 248 and 193 nm using fast-beam photofragment translational spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Harrison, Aaron W.; Ryazanov, Mikhail; Sullivan, Erin N.; Neumark, Daniel M., E-mail: dneumark@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

2016-07-14

The photodissociation dynamics of the methyl perthiyl radical (CH{sub 3}SS) have been investigated using fast-beam coincidence translational spectroscopy. Methyl perthiyl radicals were produced by photodetachment of the CH{sub 3}SS{sup −} anion followed by photodissociation at 248 nm (5.0 eV) and 193 nm (6.4 eV). Photofragment mass distributions and translational energy distributions were measured at each dissociation wavelength. Experimental results show S atom loss as the dominant (96%) dissociation channel at 248 nm with a near parallel, anisotropic angular distribution and translational energy peaking near the maximal energy available to ground state CH{sub 3}S and S fragments, indicating that the dissociation occurs along a repulsive excited state. At 193 nm, S atom loss remains the major fragmentation channel, although S{sub 2} loss becomes more competitive and constitutes 32% of the fragmentation. The translational energy distributions for both channels are very broad at this wavelength, suggesting the formation of the S{sub 2} and S atom products in several excited electronic states.

Photodissociation of the carbon monoxide dication in the {sup 3}Σ{sup −} manifold: Quantum control simulation towards the C{sup 2+} + O channel

Energy Technology Data Exchange (ETDEWEB)

Vranckx, S. [Service de Chimie Quantique et Photophysique, Université Libre de Bruxelles (ULB), CP 160/09, B-1050 Brussels (Belgium); Laboratoire de Chimie Physique (UMR 8000), Université Paris-Sud, Orsay 91405 (France); Loreau, J.; Vaeck, N. [Service de Chimie Quantique et Photophysique, Université Libre de Bruxelles (ULB), CP 160/09, B-1050 Brussels (Belgium); Meier, C. [Laboratoire Collisions Agrégats Réactivité, UMR 5589, IRSAMC, Université Toulouse III Paul Sabatier, Bât. 3R1b4, Toulouse (France); Desouter-Lecomte, M., E-mail: michele.desouter-lecomte@u-psud.fr [Laboratoire de Chimie Physique (UMR 8000), Univ. Paris Sud, Université Paris-Saclay, Orsay 91405 (France); Département de Chimie, B6c Université de Liège, Sart Tilman, 4000 Liège (Belgium)

2015-10-28

The photodissociation and laser assisted dissociation of the carbon monoxide dication X{sup 3}Π CO{sup 2+} into the {sup 3}Σ{sup −} states are investigated. Ab initio electronic structure calculations of the adiabatic potential energy curves, radial nonadiabatic couplings, and dipole moments for the X {sup 3}Π state are performed for 13 excited {sup 3}Σ{sup −} states of CO{sup 2+}. The photodissociation cross section, calculated by time-dependent methods, shows that the C{sup +} + O{sup +} channels dominate the process in the studied energy range. The carbon monoxide dication CO{sup 2+} is an interesting candidate for control because it can be produced in a single, long lived, v = 0 vibrational state due to the instability of all the other excited vibrational states of the ground {sup 3}Π electronic state. In a spectral range of about 25 eV, perpendicular transition dipoles couple this {sup 3}Π state to a manifold of {sup 3}Σ{sup −} excited states leading to numerous C{sup +} + O{sup +} channels and a single C{sup 2+} + O channel. This unique channel is used as target for control calculations using local control theory. We illustrate the efficiency of this method in order to find a tailored electric field driving the photodissociation in a manifold of strongly interacting electronic states. The selected local pulses are then concatenated in a sequence inspired by the “laser distillation” strategy. Finally, the local pulse is compared with optimal control theory.

TD-DFT Insight into Photodissociation of Co-C Bond in Coenzyme B12

Directory of Open Access Journals (Sweden)

Pawel Michal Kozlowski

2014-02-01

Full Text Available Coenzyme B12 (AdoCbl is one of the most biologically active forms of vitamin B12, and continues to be a topic of active research interest. The mechanism of Co-C bond cleavage in AdoCbl, and the corresponding enzymatic reactions are however, not well understood at the molecular level. In this work, time-dependent density functional theory (TD-DFT has been applied to investigate the photodissociation of coenzyme B12. To reduce computational cost, while retaining the major spectroscopic features of AdoCbl, a truncated model based on ribosylcobalamin (RibCbl was used to simulate Co-C photodissociation. Equilibrium geometries of RibCbl were obtained by optimization at the DFT/BP86/TZVP level of theory, and low-lying excited states were calculated by TD-DFT using the same functional and basis set. The calculated singlet states, and absorption spectra were simulated in both the gas phase, and water, using the polarizable continuum model (PCM. Both spectra were in reasonable agreement with experimental data, and potential energy curves based on vertical excitations were plotted to explore the nature of Co-C bond dissociation. It was found that a repulsive 3(σCo-C → σ*Co-C triplet state became dissociative at large Co-C bond distance, similar to a previous observation for methylcobalamin (MeCbl. Furthermore, potential energy surfaces (PESs obtained as a function of both Co-CRib and Co-NIm distances, identify the S1 state as a key intermediate generated during photoexcitation of RibCbl, attributed to a mixture of a MLCT (metal-to-ligand charge transfer and a σ bonding-ligand charge transfer (SBLCT states.

THE PHOTODISSOCIATION OF FORMALDEHYDE IN COMETS

Energy Technology Data Exchange (ETDEWEB)

Feldman, Paul D., E-mail: pfeldman@jhu.edu [Department of Physics and Astronomy, The Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD 21218 (United States)

2015-10-20

Observations of comets in the 905–1180 Å spectral band made with the Far Ultraviolet Spectroscopic Explorer in 2001 and 2004 show unusual features in the fluorescent emissions of CO and H{sub 2}. These include emission from a non-thermal high-J rotational population of CO and solar Lyα induced fluorescence from excited vibrational levels of H{sub 2}, both of which are attributed to the photodissociation of formaldehyde. In this paper we model the large number of observed H{sub 2} lines and demonstrate the dependence of the pumping on the heliocentric velocity of the comet and the solar line profiles. We also derive the rotational and vibrational populations of H{sub 2} and show that they are consistent with the results of laboratory studies of the photodissociation of H{sub 2}CO. In addition to the principal series of H i and O i, the residual spectrum is found to consist mainly of the Rydberg series of C i multiplets from which we derive the mean carbon column abundance in the coma. Fluorescent emissions from N i and N{sub 2} are also searched for.

Fast beam studies of free radical photodissociation

Energy Technology Data Exchange (ETDEWEB)

Cyr, Douglas Robert [Univ. of California, Berkeley, CA (United States)

1993-11-01

The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward.

Fast beam studies of free radical photodissociation

International Nuclear Information System (INIS)

Cyr, D.R.; California Univ., Berkeley, CA

1993-11-01

The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward

Time-resolved photodissociation of oxygen at 162 nm

International Nuclear Information System (INIS)

Trushin, Sergei A; Schmid, Wolfram E; Fuss, Werner

2011-01-01

Oxygen was excited by 10 fs pulses in the Schumann-Runge continuum at 162 nm, which is by 0.57 eV above the dissociation limit. It was probed by high-intensity ionization at 810 nm with 10 14 W cm -2 , measuring the ion yields. The O 2 + signal decays in 4.3 fs, which is much shorter than the expected time for dissociation. It is ascribed to a rapid decay of the ionization probability. In a similar time, the ion in the second excited state (with excess energy taken over from the neutral) reaches the dissociation limit, whereas this time would be much longer from the two lower ion states. In fact, the O + signal rises to a (first) maximum at 6 fs. The preference for the higher ion state is rationalized by an intermediate resonance in the neutral molecule for which the polarization dependence also provides evidence. But the shape of the O + signal is very odd: it exhibits three maxima (at 6, 29 and 53 fs) of increasing intensity, before decaying rapidly (≤3.5 fs) to a pedestal. In contrast to the first maximum, the others appear at times when there is practically no interatomic force left in the excited state. We postulate a highly repulsive doubly excited state as a resonance for interpreting the second maximum, and for the third an ion-pair state lying further outside. Comparison is made with enhanced ionization, which has often been found at large interatomic distances on multiple ionization in strong laser fields. Consistent with this mechanism is the absence of similar observations at negative delay times, where five fundamental photons act as a pump and the fifth harmonic as a probe.

Photodissociation of ethylbenzene and n-propylbenzene in a molecular beam

Science.gov (United States)

Huang, Cheng-Liang; Jiang, Jyh-Chiang; Lee, Yuan T.; Ni, Chi-Kung

2002-10-01

The photodissociation of jet-cooled ethylbenzene and n-propylbenzene at both 193 and 248 nm was studied using vacuum ultraviolet photoionization/multimass ion imaging techniques. The photofragment translational energy distributions from both the molecules obtained at 193 nm show that the probability of portioning energy to product translational energy decreases monotonically with increasing translational energy. They indicate that the dissociation occurs from the ground electronic state. However, the photofragment translational energy distributions from both molecules obtained at 248 nm contain a fast and a slow component. 75% of ethylbenzene and 80% of n-propylbenzene following the 248 nm photoexcitation dissociate from electronic excited state, resulting in the fast component. The remaining 25% of ethylbenzene and 20% of n-propylbenzene dissociate through the ground electronic state, giving rise to the slow component. A comparison with an ab initio calculation suggests that the dissociation from the first triplet state corresponds to the fast component in translational energy distribution.

Transient photoelectron spectroscopy of the dissociative Br2(1Piu) state.

Science.gov (United States)

Strasser, Daniel; Goulay, Fabien; Leone, Stephen R

2007-11-14

Photodissociation of bromine on the Br2(1Piu) state is probed with ultrafast extreme ultraviolet (53.7 nm) single-photon ionization. Time-resolved photoelectron spectra show simultaneously the depletion of ground state bromine molecules as well as the rise of Br(2P3/2) products due to 402.5 nm photolysis. A partial photoionization cross-section ratio of atomic versus molecular bromine is obtained. Transient photoelectron spectra of a dissociative wave packet on the excited state are presented in the limit of low-power-density, single-photon excitation to the dissociative state. Transient binding energy shifts of "atomic-like" photoelectron peaks are observed and interpreted as photoionization of nearly separated Br atom pairs on the Br2(1Piu) state to repulsive dissociative ionization states.

Isotope separation by selective photodissociation of glyoxal

International Nuclear Information System (INIS)

Marling, J.B.

1976-01-01

Dissociation products, mainly formaldehyde and carbon monoxide, enriched in a desired isotope of carbon, oxygen, or hydrogen are obtained by the selective photodissociation of glyoxal wherein glyoxal is subjected to electromagnetic radiation in a predetermined wavelength such that photon absorption excites and induces dissociation of only those molecules of glyoxal containing the desired isotope

Photo-electron spectroscopy using synchrotron radiation of molecular radicals and fragments produced by laser photo-dissociation

International Nuclear Information System (INIS)

Nahon, Laurent

1991-01-01

This research thesis reports the combined use of a laser and of a synchrotron radiation in order to respectively photo-dissociate a molecule and to photo-ionize fragments which are analysed by photo-electron spectroscopy. This association allows, on the one hand, radical photo-ionization to be studied, and, on the other hand, polyatomic molecule photo-dissociation to be studied. The author studied the photo-excitation and/or photo-ionization in layer 4d (resp. 3d) of atomic iodine (resp. bromine) produced almost complete laser photo-dissociation of I_2 (resp. Br_2). He discuses the processes of relaxation of transitions from valence 4d to 5p (resp. 3d to 4p) which occur either by direct self-ionization or by resonant Auger effect, and reports the study of photo-dissociation of s-tetrazine (C_2N_4H_2) [fr

An alternative laser driven photodissociation mechanism of pyrrole via π*1σ/S0 conical intersection

Science.gov (United States)

Nandipati, K. R.; Lan, Z.; Singh, H.; Mahapatra, S.

2017-06-01

A first principles quantum dynamics study of N-H photodissociation of pyrrole on the S0-1π σ*(A12) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the π*1σ state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the π*1σ photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation.

Photodissociation dynamics of CH3C(O)SH in argon matrix: A QM/MM nonadiabatic dynamics simulation

Science.gov (United States)

Xia, Shu-Hua; Liu, Xiang-Yang; Fang, Qiu; Cui, Ganglong

2015-11-01

In this work, we have first employed the combined quantum mechanics/molecular mechanics (QM/MM) method to study the photodissociation mechanism of thioacetic acid CH3C(O)SH in the S1, T1, and S0 states in argon matrix. CH3C(O)SH is treated quantum mechanically using the complete active space self-consistent field and complete active space second-order perturbation theory methods; argon matrix is described classically using Lennard-Jones potentials. We find that the C-S bond fission is predominant due to its small barriers of ca. 3.0 and 1.0 kcal/mol in the S1 and T1 states. It completely suppresses the nearby C—C bond fission. After the bond fission, the S1 radical pair of CH3CO and SH can decay to the S0 and T1 states via internal conversion and intersystem crossing, respectively. In the S0 state, the radical pair can either recombine to form CH3C(O)SH or proceed to form molecular products of CH2CO and H2S. We have further employed our recently developed QM/MM generalized trajectory-based surface-hopping method to simulate the photodissociation dynamics of CH3C(O)SH. In 1 ps dynamics simulation, 56% trajectories stay at the Franck-Condon region; the S1 C—S bond fission takes place in the remaining 44% trajectories. Among all nonadiabatic transitions, the S1 → S0 internal conversion is major (55%) but the S1 → T1 intersystem crossing is still comparable and cannot be ignored, which accounts for 28%. Finally, we have found a radical channel generating the molecular products of CH2CO and H2S, which is complementary to the concerted molecular channel. The present work sets the stage for simulating photodissociation dynamics of similar thio-carbonyl systems in matrix.

Potential energy surface from spectroscopic data in the photodissociation of polyatomic molecules

International Nuclear Information System (INIS)

Kim, Hwa Joong; Kim, Young Sik

2001-01-01

The time-dependent tracking inversion method is studied to extract the potential energy surface of the electronic excited state in the photodissociation of triatomic molecules. Based on the relay of the regularized inversion procedure and time-dependent wave packet propagation, the algorithm extracts the underlying potential energy surface piece by tracking the time-dependent data, which can be synthesized from Raman excitation profiles. We have demonstrated the algorithm to extract the potential energy surface of electronic excited state for NO 2 molecule where the wave packet split on a saddle-shaped surface. Finally, we describe the merits of the time-dependent tracking inversion method compared with the time-dependent inversion method and discussed several extensions of the algorithm

Photodissociation dynamics of CH{sub 3}C(O)SH in argon matrix: A QM/MM nonadiabatic dynamics simulation

Energy Technology Data Exchange (ETDEWEB)

Xia, Shu-Hua; Liu, Xiang-Yang; Fang, Qiu; Cui, Ganglong, E-mail: ganglong.cui@bnu.edu.cn [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)

2015-11-21

In this work, we have first employed the combined quantum mechanics/molecular mechanics (QM/MM) method to study the photodissociation mechanism of thioacetic acid CH{sub 3}C(O)SH in the S{sub 1}, T{sub 1}, and S{sub 0} states in argon matrix. CH{sub 3}C(O)SH is treated quantum mechanically using the complete active space self-consistent field and complete active space second-order perturbation theory methods; argon matrix is described classically using Lennard-Jones potentials. We find that the C-S bond fission is predominant due to its small barriers of ca. 3.0 and 1.0 kcal/mol in the S{sub 1} and T{sub 1} states. It completely suppresses the nearby C—C bond fission. After the bond fission, the S{sub 1} radical pair of CH{sub 3}CO and SH can decay to the S{sub 0} and T{sub 1} states via internal conversion and intersystem crossing, respectively. In the S{sub 0} state, the radical pair can either recombine to form CH{sub 3}C(O)SH or proceed to form molecular products of CH{sub 2}CO and H{sub 2}S. We have further employed our recently developed QM/MM generalized trajectory-based surface-hopping method to simulate the photodissociation dynamics of CH{sub 3}C(O)SH. In 1 ps dynamics simulation, 56% trajectories stay at the Franck-Condon region; the S{sub 1} C—S bond fission takes place in the remaining 44% trajectories. Among all nonadiabatic transitions, the S{sub 1} → S{sub 0} internal conversion is major (55%) but the S{sub 1} → T{sub 1} intersystem crossing is still comparable and cannot be ignored, which accounts for 28%. Finally, we have found a radical channel generating the molecular products of CH{sub 2}CO and H{sub 2}S, which is complementary to the concerted molecular channel. The present work sets the stage for simulating photodissociation dynamics of similar thio-carbonyl systems in matrix.

An alternative laser driven photodissociation mechanism of pyrrole via πσ*1∕S0 conical intersection.

Science.gov (United States)

Nandipati, K R; Lan, Z; Singh, H; Mahapatra, S

2017-06-07

A first principles quantum dynamics study of N-H photodissociation of pyrrole on the S 0 - 1 πσ * (A21) coupled electronic states is carried out with the aid of an optimally designed UV-laser pulse. A new photodissociation path, as compared to the conventional barrier crossing on the πσ*1 state, opens up upon electronic transitions under the influence of pump-dump laser pulses, which efficiently populate both the dissociation channels. The interplay of electronic transitions due both to vibronic coupling and the laser pulse is observed in the control mechanism and discussed in detail. The proposed control mechanism seems to be robust, and not discussed in the literature so far, and is expected to trigger future experiments on the πσ*1 photochemistry of molecules of chemical and biological importance. The design of the optimal pulses and their application to enhance the overall dissociation probability is carried out within the framework of optimal control theory. The quantum dynamics of the system in the presence of pulse is treated by solving the time-dependent Schrödinger equation in the semi-classical dipole approximation.

UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

Science.gov (United States)

Hansen, Christopher S.; Kirk, Benjamin B.; Blanksby, Stephen J.; O'Hair, Richard. A. J.; Trevitt, Adam J.

2013-06-01

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag2 + is compared with a literature spectrum as a further benchmark.

Photodissociation spectroscopy of the Mg + -CO2 complex and its isotopic analogs

Science.gov (United States)

Yeh, C. S.; Willey, K. F.; Robbins, D. L.; Pilgrim, J. S.; Duncan, M. A.

1993-02-01

Mg+-CO2 ion-molecule cluster complexes are produced by laser vaporization in a pulsed nozzle cluster source. The vibronic spectroscopy in these complexes is studied with mass-selected photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer. Two excited electronic states are observed (2) 2Σ+ and 2Π. The 2Π state has a vibrational progression in the metal-CO2 stretching mode (ωe'=381.8 cm-1). The complexes are linear (Mg+-OCO) and are bound by the charge-quadrupole interaction. The dissociation energy (D0`) is 14.7 kcal/mol. Corresponding spectra are measured for each of the 24, 25, and 26 isotopes of magnesium. These results are compared to theoretical predictions made by Bauschlicher and co-workers.

Photodissociation and photoionisation of atoms and molecules of astrophysical interest

Science.gov (United States)

Heays, A. N.; Bosman, A. D.; van Dishoeck, E. F.

2017-06-01

A new collection of photodissociation and photoionisation cross sections for 102 atoms and molecules of astrochemical interest has been assembled, along with a brief review of the basic physical processes involved. These have been used to calculate dissociation and ionisation rates, with uncertainties, in a standard ultraviolet interstellar radiation field (ISRF) and for other wavelength-dependent radiation fields, including cool stellar and solar radiation, Lyman-α dominated radiation, and a cosmic-ray induced ultraviolet flux. The new ISRF rates generally agree within 30% with our previous compilations, with a few notable exceptions. Comparison with other databases such as PHIDRATES is made. The reduction of rates in shielded regions was calculated as a function of dust, molecular and atomic hydrogen, atomic C, and self-shielding column densities. The relative importance of these shielding types depends on the atom or molecule in question and the assumed dust optical properties. All of the new data are publicly available from the Leiden photodissociation and ionisation database. Sensitivity of the calculated rates to variation of temperature and isotope, and uncertainties in measured or calculated cross sections, are tested and discussed. Tests were conducted on the new rates with an interstellar-cloud chemical model, and find general agreement (within a factor of two) in abundances obtained with the previous iteration of the Leiden database assuming an ISRF, and order-of-magnitude variations assuming various kinds of stellar radiation. The newly parameterised dust-shielding factors makes a factor-of-two difference to many atomic and molecular abundances relative to parameters currently in the UDfA and KIDA astrochemical reaction databases. The newly-calculated cosmic-ray induced photodissociation and ionisation rates differ from current standard values up to a factor of 5. Under high temperature and cosmic-ray-flux conditions the new rates alter the equilibrium

Atomic carbon emission from photodissociation of CO2. [planetary atmospheric chemistry

Science.gov (United States)

Wu, C. Y. R.; Phillips, E.; Lee, L. C.; Judge, D. L.

1978-01-01

Atomic carbon fluorescence, C I 1561, 1657, and 1931 A, has been observed from photodissociation of CO2, and the production cross sections have been measured. A line emission source provided the primary photons at wavelengths from threshold to 420 A. The present results suggest that the excited carbon atoms are produced by total dissociation of CO2 into three atoms. The cross sections for producing the O I 1304-A fluorescence through photodissociation of CO2 are found to be less than 0.01 Mb in the wavelength region from 420 to 835 A. The present data have implications with respect to photochemical processes in the atmospheres of Mars and Venus.

Controlling the branching ratio of photodissociation using aligned molecules

DEFF Research Database (Denmark)

Larsen, J.J.; Wendt-Larsen, I.; Stapelfeldt, H.

1999-01-01

Using a sample of iodine molecules, aligned by a strong, linearly polarized laser pulse, we control the branching ratio of the I+I and I+I* photodissociation channels by a factor of 26. The control relies on selective photoexcitation of two potential curves that each correlate adiabatically...

Quantum chemical molecular dynamical investigation of alkyl nitrite photo-dissociated on copper surfaces

International Nuclear Information System (INIS)

Wang Xiaojing; Wang Wei; Han Peilin; Kubo, Momoji; Miyamoto, Akira

2008-01-01

An accelerated quantum chemical molecular dynamical code 'Colors-Excite' was used to investigate the photolysis of alkyl nitrites series, RONO (R=CH 3 and C(CH 3 ) 3 ) on copper surfaces. Our calculations showed that the photo-dissociated processes are associated with the alkyl substituents of RONO when adsorbed on copper surfaces. For R=CH 3 , a two-step photolysis reaction occurred, yielding diverse intermediate products including RO radical, NO, and HNO, consistent with those reported in gas phase. While for R=C(CH 3 ) 3 , only one-step photolysis reaction occurred and gave intermediate products of RO radical and NO. Consequently, pure RO species were achieved to adsorb on metal surfaces by removing the NO species in photolysis reaction. The detailed photo-dissociated behaviors of RONO on copper surfaces with different alkyl substituents which are uncovered by the present simulation can be extended to explain the diverse dissociative mechanism experimentally observed. The quantum chemical molecular dynamical code 'Colors-Excite' is proved to be highly applicable to the photo-dissociations on metal surfaces

Combining UV photodissociation with electron transfer for peptide structure analysis

Czech Academy of Sciences Publication Activity Database

Shaffer, C. J.; Marek, Aleš; Pepin, R.; Slováková, K.; Tureček, F.

2015-01-01

Roč. 50, č. 3 (2015), s. 470-475 ISSN 1076-5174 Institutional support: RVO:61388963 Keywords : electron transfer dissociation * laser photodissociation * peptide ions * cation radical * chromophores * isomer distinction Subject RIV: CE - Biochemistry Impact factor: 2.541, year: 2015

Control of HOD photodissociation dynamics via bond-selective infrared multiphoton excitation and a femtosecond ultraviolet laser pulse

DEFF Research Database (Denmark)

Amstrup, Bjarne; Henriksen, Niels Engholm

1992-01-01

moment, excites the molecule to a dissociative electronic state. We consider the HOD molecule which is ideal due to the local mode structure of the vibrational states. It is shown that selective and localized bond stretching can be created in simple laser fields. When such a nonstationary vibrating HOD...... molecule is photodissociated with a short laser pulse (~5 fs) complete selectivity between the channels H+OD and D+OH is observed over the entire absorption band covering these channels. The Journal of Chemical Physics is copyrighted by The American Institute of Physics....

Nonadiabatic effects in C-Br bond scission in the photodissociation of bromoacetyl chloride

International Nuclear Information System (INIS)

Valero, Rosendo; Truhlar, Donald G.

2006-01-01

Bromoacetyl chloride photodissociation has been interpreted as a paradigmatic example of a process in which nonadiabatic effects play a major role. In molecular beam experiments by Butler and co-workers [J. Chem. Phys. 95, 3848 (1991); J. Chem. Phys. 97, 355 (1992)], BrCH 2 C(O)Cl was prepared in its ground electronic state (S 0 ) and excited with a laser at 248 nm to its first excited singlet state (S 1 ). The two main ensuing photoreactions are the ruptures of the C-Cl bond and of the C-Br bond. A nonadiabatic model was proposed in which the C-Br scission is strongly suppressed due to nonadiabatic recrossing at the barrier formed by the avoided crossing between the S 1 and S 2 states. Recent reduced-dimensional dynamical studies lend support to this model. However, another interpretation that has been given for the experimental results is that the reduced probability of C-Br scission is a consequence of incomplete intramolecular energy redistribution. To provide further insight into this problem, we have studied the energetically lowest six singlet electronic states of bromoacetyl chloride by using an ab initio multiconfigurational perturbative electronic structure method. Stationary points (minima and saddle points) and minimum energy paths have been characterized on the S 0 and S 1 potential energy surfaces. The fourfold way diabatization method has been applied to transform five adiabatic excited electronic states to a diabatic representation. The diabatic potential energy matrix of the first five excited singlet states has been constructed along several cuts of the potential energy hypersurfaces. The thermochemistry of the photodissociation reactions and a comparison with experimental translational energy distributions strongly suggest that nonadiabatic effects dominate the C-Br scission, but that the reaction proceeds along the energetically allowed diabatic pathway to excited-state products instead of being nonadiabatically suppressed. This conclusion is

Characteristic analysis of laser isotope separation process by two-step photodissociation method

International Nuclear Information System (INIS)

Okamoto, Tsuyoshi; Suzuki, Atsuyuki; Kiyose, Ryohei

1981-01-01

A large number of laser isotope separation experiments have been performed actively in many countries. In this paper, the selective two-step photodissociation method is chosen and simultaneous nonlinear differential equations that express the separation process are solved directly by using computer. Predicted separation factors are investigated in relation to the incident pulse energy and the concentration of desired molecules. Furthermore, the concept of separative work is used to evaluate the results of separation for this method. It is shown from an example of numerical calculation that a very large separation factor can be obtained if the concentration of desired molecules is lowered and two laser pulses to be closely synchronized are not always required in operation for the photodissociation of molecules. (author)

Correlation functions for fully or partially state-resolved reactive scattering calculations

International Nuclear Information System (INIS)

Manthe, Uwe; Welsch, Ralph

2014-01-01

Flux correlation functions and the quantum transition state concept are important tools for the accurate description of polyatomic reaction processes. Combined with the multi-configurational time-dependent Hartree approach, they facilitate rigorous full-dimensional calculations of cumulative and initial-state selected reaction probabilities for six atom reactions. In recent work [R. Welsch, F. Huarte-Larrañaga, and U. Manthe, J. Chem. Phys. 136, 064117 (2012)], an approach which allows one to calculate also state-to-state reaction probabilities within the quantum transition state concept has been introduced. This article presents further developments. Alternative generalized flux correlation functions are introduced and discussed. Equations for the calculation of fully state-resolved differential cross section using arbitrary definitions of the body fixed frame are derived. An approach for the efficient calculation of partially state-resolved observables as a function of the collision energy is introduced. Finally, numerical test studying the D + H 2 reaction illustrate important aspects of the formalism

Effect of linear chirp on strong field photodissociation of H+2

International Nuclear Information System (INIS)

Prabhudesai, Vaibhav; Natan, Adi; Bruner, Barry; Silberberg, Yaron; Lev, Uri; Heber, Oded; Strasser, Daniel; Schwalm, Dirk; Zajfman, Daniel; Ben-Itzhak, Itzik

2011-01-01

We report the experimental findings of a systematic study of the effect of linear chirp on strong field photodissociation of H + 2 . For vibrational levels around or above the one photon crossing, the effect manifests itself in terms of a shift in the kinetic energy release (KER) peaks. The peaks shift up for negative chirp whereas they shift down for positive chirp. The measurements are carried out by varying two of the three laser pulse characteristics, energy, pulse peak intensity and linear chirp, while keeping the third constant. The shifts in the KER peaks are found to be intensity dependent for a given value of chirp. However, in the last two cases (i.e., fixed pulsed energy and fixed pulse peak intensity), they are found to be independent of the chirp magnitude. The results are understood on the basis of saturation of photodissociation probabilities for these levels.

Classical photodissociation dynamics with Bohr quantization: Application to the fragmentation of a van der Waals cluster

International Nuclear Information System (INIS)

Arbelo-González, W.; Bonnet, L.; Larrégaray, P.; Rayez, J.-C.; Rubayo-Soneira, J.

2012-01-01

Graphical abstract: A recent classical description of photodissociation dynamics in a quantum spirit is applied for the first time to a realistic process, the fragmentation of NeBr 2 . Highlights: ► The photo-dissociation of NeBr 2 is studied by means of two approaches. ► The first is the standard classical one with Gaussian binning. ► The second is a new method applied for the first time to a realistic system. ► The new method leads to exactly the same results as the standard one. ► However, it requires about 10 times less trajectories in the present case. - Abstract: The recent classical dynamical approach of photodissociations with Bohr quantization [L. Bonnet, J. Chem. Phys. 133 (2010) 174108] is applied for the first time to a realistic process, the photofragmentation of the van der Waals cluster NeBr 2 . We illustrate the fact that this approach, formally equivalent to the standard one, may be numerically much more efficient.

Ultrafast Photodissociation Dynamics of the F State of Sulfur Dioxide by Femtosecond Time-Resolved Pump-Probe Method

International Nuclear Information System (INIS)

Zhang Dong-Dong; Ni Qiang; Luo Si-Zuo; Zhang Jing; Liu Hang; Xu Hai-Feng; Jin Ming-Xing; Ding Da-Jun

2011-01-01

A femtosecond pump-probe method is employed to study the dissociation dynamics of sulfur dioxide. SO 2 molecules are excited to the F state by absorbing two photons of 267 nm femtosecond laser pulses, and ionized by 400 nm laser pulses at different delay times between the two lasers. Transients of both parent ions (SO + 2 ) and the fragment ions (SO + , S + and O + ) are observed. The SO + 2 transient can be well fitted to a biexponential decay comprising a fast and a slow component of 280 fs and 2.97 ps lifetimes, respectively. The SO + transient consists of two growth components of 270 fs and 2.50 ps. The results clearly show that the F state of SO 2 dissociates along an S-O bond. The transients of S + and O + , however, have different behavior, which consist of a fast growth and a long decay component. A possible mechanism of the fragment formation is discussed to understand the dissociation dynamics of the F state of SO 2 . (atomic and molecular physics)

Study of the photodissociation of a CdSe nanocrystal beam by means of photoluminescence and Raman scattering

CERN Document Server

Orii, T; Onari, S; Kaito, S I; Arai, T

1997-01-01

We developed an apparatus that enables us to perform optical measurements of nanocrystals suspended in vacuum. CdSe nanocrystals were produced by a gas evaporation method, and nanocrystal beams were then formed using an inert-gas flow with differential pumping. We measured photoluminescence spectra of the nanocrystal beams with excitations of various photon energies and powers. For a low excitation power, edge emission of the CdSe nanocrystal beam was observed. With increase of the laser power, Raman lines of Se dimers emitted due to the photodissociation of CdSe nanocrystals were observed. It was found that the thresholds of the excitation laser fluence for the photodissociation of CdSe nanocrystals were much smaller than the thresholds of laser fluence for the laser-induced emission of Se atoms from bulk CdSe. The electronic process is dominant in the photodissociation of CdSe nanocrystals whose surfaces are completely free. We suggest that the effective supply of carriers confined in nanocrystals to the su...

Energy storage and redistribution in molecules

International Nuclear Information System (INIS)

Hinze, J.

1983-01-01

This book presents information on the following topics: chemistry and spectroscopy of molecules at high levels of excitation; energy and phase randomization in large molecules as probed by laser spectroscopy; intramolecular processes in isolated polyatomic molecules; pulse-probe measurements in low-temperature, low-pressure SF 6 ; the photodissociation dynamics of H 2 S and CF 3 NO; photofragment spectroscopy of the NO 2 dissociation; preparation, laser spectroscopy and predissociation of alkali dimers in supersonic nozzle beams; excited states of small molecules - collisional quenching and photodissociation; quantum-state-resolved scattering of lithium hydride; and molecular negative ions

Photodissociation of spatially aligned acetaldehyde cations.

Science.gov (United States)

Lee, Suk Kyoung; Silva, Ruchira; Kim, Myung Hwa; Shen, Lei; Suits, Arthur G

2007-07-26

Photofragment translational energy and angular distributions are reported for the photodissociation of acetaldehyde cations in the wavelength range 354-363 nm obtained using the DC slice ion imaging technique. Vibrationally selected parent ions were produced by 2+1 resonance-enhanced multiphoton ionization (REMPI) via the 3sCH3CO+, and CH4+. The angular distributions reveal that all product channels have a predominantly parallel recoil anisotropy although the lower beta2 parameter of CH3CO+ indicates the concomitant presence of a perpendicular component. Furthermore, the distinct angular distribution of the CH3CO+ fragments shows a large value of the higher order Legendre polynomial term, providing evidence that acetaldehyde cations are spatially aligned during the ionization process.

The effects of polycyclic aromatic hydrocarbons on the chemistry of photodissociation regions

NARCIS (Netherlands)

Bakes, ELO; Tielens, AGGM

1998-01-01

We have investigated the effects of including polycylic aromatic hydrocarbons (PAHs) on the abundance of neutral atoms and molecules for two typical photodissociation regions (PDRs): a high-density case (the Orion complex) and a low-density case. PAHs provide a large surface area for chemistry

Synergistic effects for the TiO2/RuO2/Pt photodissociation of water

Energy Technology Data Exchange (ETDEWEB)

Blondel, G; Harriman, A; Williams, D

1983-07-01

Compressed discs of naked TiO2 or TiO2 coated with a thin film of a noble metal (e.g. Pt) do not photodissociate water upon illumination with UV light, but small amounts of H2 are generated if the TiO2 has been reduced in a stream of H2 at 600 C. Discs prepared from mixtures of TiO2/RuO2 facilitate the UV photodissociation of water into H2 and O2 although the yields are very low. When a thin (about 9 nm) film of Pt is applied to the TiO2/RuO2 discs, the yields of H2 and O2 observed upon irradiation with UV light are improved drastically. 25 references.

Transition state region in the A-Band photodissociation of allyl iodide—A femtosecond extreme ultraviolet transient absorption study

Energy Technology Data Exchange (ETDEWEB)

Bhattacherjee, Aditi, E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu; Attar, Andrew R., E-mail: abhattacherjee@berkeley.edu, E-mail: andrewattar@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Leone, Stephen R., E-mail: srl@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States)

2016-03-28

Femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy based on a high-harmonic generation source is used to study the 266 nm induced A-band photodissociation dynamics of allyl iodide (CH{sub 2} =CHCH{sub 2}I). The photolysis of the C—I bond at this wavelength produces iodine atoms both in the ground ({sup 2}P{sub 3/2}, I) and spin-orbit excited ({sup 2}P{sub 1/2}, I*) states, with the latter as the predominant channel. Using XUV absorption at the iodine N{sub 4/5} edge (45–60 eV), the experiments constitute a direct probe of not only the long-lived atomic iodine reaction products but also the fleeting transition state region of the repulsive n{sub I}σ{sup ∗}{sub C—I} excited states. Specifically, three distinct features are identified in the XUV transient absorption spectrum at 45.3 eV, 47.4 eV, and 48.4 eV (denoted transients A, B, and C, respectively), which arise from the repulsive valence-excited nσ{sup ∗} states and project onto the high-lying core-excited states of the dissociating molecule via excitation of 4d(I) core electrons. Transients A and B originate from 4d(I) → n(I) core-to-valence transitions, whereas transient C is best assigned to a 4d(I) →σ{sup ∗}(C—I) transition. The measured differential absorbance of these new features along with the I/I* branching ratios known from the literature is used to suggest a more definitive assignment, albeit provisional, of the transients to specific dissociative states within the A-band manifold. The transients are found to peak around 55 fs–65 fs and decay completely by 145 fs–185 fs, demonstrating the ability of XUV spectroscopy to map the evolution of reactants into products in real time. The similarity in the energies of transients A and B with analogous features observed in methyl iodide [Attar et al. J. Phys. Chem. Lett. 6, 5072, (2015)] together with the new observation of transient C in the present work provides a more complete picture of the valence electronic

Signatures of non-adiabatic dynamics in the fine-structure state distributions of the OH(X~/A~) products in the B-band photodissociation of H2O

International Nuclear Information System (INIS)

Zhou, Linsen; Xie, Daiqian; Guo, Hua

2015-01-01

A detailed quantum mechanical characterization of the photodissociation dynamics of H 2 O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X ~ /A ~ ) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X ~ , v = 0) exhibit very different characteristics. The A′ states, produced mostly via the B ~ →X ~ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B ~ →A ~ Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X ~ ) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B ~ →X ~ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(A ~ ) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces

Signatures of non-adiabatic dynamics in the fine-structure state distributions of the OH(X̃/Ã) products in the B-band photodissociation of H2O.

Science.gov (United States)

Zhou, Linsen; Xie, Daiqian; Guo, Hua

2015-03-28

A detailed quantum mechanical characterization of the photodissociation dynamics of H2O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X̃/Ã) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X̃, v = 0) exhibit very different characteristics. The A' states, produced mostly via the B̃→X̃ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B̃→Ã Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X̃) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B̃→X̃ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(Ã) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.

Particle-Resolved Modeling of Aerosol Mixing State in an Evolving Ship Plume

Science.gov (United States)

Riemer, N. S.; Tian, J.; Pfaffenberger, L.; Schlager, H.; Petzold, A.

2011-12-01

The aerosol mixing state is important since it impacts the particles' optical and CCN properties and thereby their climate impact. It evolves continuously during the particles' residence time in the atmosphere as a result of coagulation with other particles and condensation of secondary aerosol species. This evolution is challenging to represent in traditional aerosol models since they require the representation of a multi-dimensional particle distribution. While modal or sectional aerosol representations cannot practically resolve the aerosol mixing state for more than a few species, particle-resolved models store the composition of many individual aerosol particles directly. They thus sample the high-dimensional composition state space very efficiently and so can deal with tens of species, fully resolving the mixing state. Here we use the capabilities of the particle-resolved model PartMC-MOSAIC to simulate the evolution of particulate matter emitted from marine diesel engines and compare the results to aircraft measurements made in the English Channel in 2007 as part of the European campaign QUANTIFY. The model was initialized with values of gas concentrations and particle size distributions and compositions representing fresh ship emissions. These values were obtained from a test rig study in the European project HERCULES in 2006 using a serial four-stroke marine diesel engine operating on high-sulfur heavy fuel oil. The freshly emitted particles consisted of sulfate, black carbon, organic carbon and ash. We then tracked the particle population for several hours as it evolved undergoing coagulation, dilution with the background air, and chemical transformations in the aerosol and gas phase. This simulation was used to compute the evolution of CCN properties and optical properties of the plume on a per-particle basis. We compared our results to size-resolved data of aged ship plumes from the QUANTIFY Study in 2007 and showed that the model was able to reproduce

Communication: On the competition between adiabatic and nonadiabatic dynamics in vibrationally mediated ammonia photodissociation in its A band

Energy Technology Data Exchange (ETDEWEB)

Xie, Changjian [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Zhu, Xiaolei; Yarkony, David R., E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Ma, Jianyi, E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, Sichuan 610065 (China); Xie, Daiqian, E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Guo, Hua, E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

2015-03-07

Non-adiabatic processes play an important role in photochemistry, but the mechanism for conversion of electronic energy to chemical energy is still poorly understood. To explore the possibility of vibrational control of non-adiabatic dynamics in a prototypical photoreaction, namely, the A-band photodissociation of NH{sub 3}(X{sup ~1}A{sub 1}), full-dimensional state-to-state quantum dynamics of symmetric or antisymmetric stretch excited NH{sub 3}(X{sup ~1}A{sub 1}) is investigated on recently developed coupled diabatic potential energy surfaces. The experimentally observed H atom kinetic energy distributions are reproduced. However, contrary to previous inferences, the NH{sub 2}(A{sup ~2}A{sub 1})/NH{sub 2}(X{sup ~2}B{sub 1}) branching ratio is found to be small regardless of the initial preparation of NH{sub 3}(X{sup ~1}A{sub 1}), while the internal state distribution of the preeminent fragment, NH{sub 2}(X{sup ~2}B{sub 1}), is found to depend strongly on the initial vibrational excitation of NH{sub 3}(X{sup ~1}A{sub 1}). The slow H atoms in photodissociation mediated by the antisymmetric stretch fundamental state are due to energy sequestered in the internally excited NH{sub 2}(X{sup ~2}B{sub 1}) fragment, rather than in NH{sub 2}(A{sup ~2}A{sub 1}) as previously proposed. The high internal excitation of the NH{sub 2}(X{sup ~2}B{sub 1}) fragment is attributed to the torques exerted on the molecule as it passes through the conical intersection seam to the ground electronic state of NH{sub 3}. Thus in this system, contrary to previous assertions, the control of electronic state branching by selective excitation of ground state vibrational modes is concluded to be ineffective. The juxtaposition of precise quantum mechanical results with complementary results based on quasi-classical surface hopping trajectories provides significant insights into the non-adiabatic process.

Internal energy of HCl upon photolysis of 2-chloropropene at 193 nm investigated with time-resolved Fourier-transform spectroscopy and quasiclassical trajectories

International Nuclear Information System (INIS)

Chang, C.-M.; Huang, Y.-H.; Liu, S.-Y.; Lee, Y.-P.; Pombar-Perez, Marta; Martinez-Nunez, Emilio; Vazquez, Saulo A.

2008-01-01

Following photodissociation of 2-chloropropene (H 2 CCClCH 3 ) at 193 nm, vibration-rotationally resolved emission spectra of HCl (υ≤6) in the spectral region of 1900-2900 cm -1 were recorded with a step-scan time-resolved Fourier-transform spectrometer. All vibrational levels show a small low-J component corresponding to ∼400 K and a major high-J component corresponding to 7100-18 700 K with average rotational energy of 39± 3 11 kJ mol -1 . The vibrational population of HCl is inverted at υ=2, and the average vibrational energy is 86±5 kJ mol -1 . Two possible channels of molecular elimination producing HCl+propyne or HCl+allene cannot be distinguished positively based on the observed internal energy distribution of HCl. The observed rotational distributions fit qualitatively with the distributions of both channels obtained with quasiclassical trajectories (QCTs), but the QCT calculations predict negligible populations for states at small J. The observed vibrational distribution agrees satisfactorily with the total QCT distribution obtained as a weighted sum of contributions from both four-center elimination channels. Internal energy distributions of HCl from 2-chloropropene and vinyl chloride are compared.

Effect of linear chirp on strong field photodissociation of H{sup +}{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Prabhudesai, Vaibhav; Natan, Adi; Bruner, Barry; Silberberg, Yaron; Lev, Uri; Heber, Oded; Strasser, Daniel; Schwalm, Dirk; Zajfman, Daniel [Weizmann Institute of Science, 76100 (Israel); Ben-Itzhak, Itzik [Kansas State University, Kansas (United States)

2011-10-15

We report the experimental findings of a systematic study of the effect of linear chirp on strong field photodissociation of H{sup +}{sub 2}. For vibrational levels around or above the one photon crossing, the effect manifests itself in terms of a shift in the kinetic energy release (KER) peaks. The peaks shift up for negative chirp whereas they shift down for positive chirp. The measurements are carried out by varying two of the three laser pulse characteristics, energy, pulse peak intensity and linear chirp, while keeping the third constant. The shifts in the KER peaks are found to be intensity dependent for a given value of chirp. However, in the last two cases (i.e., fixed pulsed energy and fixed pulse peak intensity), they are found to be independent of the chirp magnitude. The results are understood on the basis of saturation of photodissociation probabilities for these levels.

Photodissociation of HCN and HNC isomers in the 7-10 eV energy range

Energy Technology Data Exchange (ETDEWEB)

Chenel, Aurelie; Roncero, Octavio, E-mail: octavio.roncero@csic.es [Instituto de Física Fundamental (IFF-CSIC), C.S.I.C., Serrano 123, 28006 Madrid (Spain); Aguado, Alfredo [Departamento de Química Física Aplicada (UAM), Unidad Asociada a IFF-CSIC, Facultad de Ciencias Módulo 14, Universidad Autónoma de Madrid, 28049 Madrid (Spain); Agúndez, Marcelino; Cernicharo, José [Instituto de Ciencia de Materiales de Madrid, CSIC, C/ Sor Juana Inés de la Cruz 3, 28049 Cantoblanco (Spain)

2016-04-14

The ultraviolet photoabsorption spectra of the HCN and HNC isomers have been simulated in the 7-10 eV photon energy range. For this purpose, the three-dimensional adiabatic potential energy surfaces of the 7 lowest electronic states, and the corresponding transition dipole moments, have been calculated, at multireference configuration interaction level. The spectra are calculated with a quantum wave packet method on these adiabatic potential energy surfaces. The spectra for the 3 lower excited states, the dissociative electronic states, correspond essentially to predissociation peaks, most of them through tunneling on the same adiabatic state. The 3 higher electronic states are bound, hereafter electronic bound states, and their spectra consist of delta lines, in the adiabatic approximation. The radiative lifetime towards the ground electronic states of these bound states has been calculated, being longer than 10 ns in all cases, much longer that the characteristic predissociation lifetimes. The spectra of HCN is compared with the available experimental and previous theoretical simulations, while in the case of HNC there are no previous studies to our knowledge. The spectrum for HNC is considerably more intense than that of HCN in the 7-10 eV photon energy range, which points to a higher photodissociation rate for HNC, compared to HCN, in astrophysical environments illuminated by ultraviolet radiation.

Probing the ignored elimination channel of Br2 in the 248 nm photodissociation of 1,1-dibromoethylene by cavity ring-down absorption spectroscopy.

Science.gov (United States)

Lee, Ping-Chen; Tsai, Po-Yu; Hsiao, Ming-Kai; Lin, King-Chuen; Huang, C H; Chang, A H H

2009-03-09

In the photodissociation of 1,1-C(2)H(2)Br(2) at 248 nm, the Br(2) elimination channel is probed by using cavity ring-down absorption spectroscopy (CRDS). In terms of spectral simulation, the vibrational population ratio of Br(2)(v = 1)/Br(2)(v = 0) is found to be 0.55+/-0.05, which indicates that the Br(2) fragment is vibrationally hot. The rotational population is thermally equilibrated with a Boltzmann temperature of 349+/-38 K. According to ab initio potential energy calculations, the obtained fragments are anticipated to result primarily from photodissociation of the ground electronic state that undergoes 1) H migration followed by three-center elimination, and 2) isomerization forming either trans- or cis-1,2-C(2)H(2)Br(2) from which Br(2) is eliminated. RRKM calculations predict that the Br(2) dissociation rates through the ground singlet state prevail over those through the triplet state. Measurements of temperature and Ar pressure dependence are examined to support the proposed pathway via internal conversion. The quantum yield for the Br(2) elimination reaction is determined to be 0.07+/-0.04. This result is smaller than that obtained in 1,2-C(2)H(2)Br(2), probably because the dissociation rates are slowed in the isomerization stage.

Discrimination of optical coherent states using a photon number resolving detector

DEFF Research Database (Denmark)

Wittmann, C.; Andersen, Ulrik Lund; Leuchs, G.

2010-01-01

The discrimination of non-orthogonal quantum states with reduced or without errors is a fundamental task in quantum measurement theory. In this work, we investigate a quantum measurement strategy capable of discriminating two coherent states probabilistically with significantly smaller error...... probabilities than can be obtained using non-probabilistic state discrimination. We find that appropriate postselection of the measurement data of a photon number resolving detector can be used to discriminate two coherent states with small error probability. We compare our new receiver to an optimal...

Imaging of rotational wave-function in photodissociation of rovibrationally excited HCl molecules

Czech Academy of Sciences Publication Activity Database

Grygoryeva, Kateřina; Rakovský, Jozef; Votava, Ondřej; Fárník, Michal

2017-01-01

Roč. 147, č. 1 (2017), č. článku 013901. ISSN 0021-9606 R&D Projects: GA ČR GA14-08937S; GA ČR GA13-11635S Institutional support: RVO:61388955 Keywords : Angular distribution * Chemical reactions * Photodissociation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 2.965, year: 2016

Photodissociation thresholds of OH produced from CH sub 3 OH in solid neon and argon

CERN Document Server

Cheng, B M; Lo, W J; Lee, Y P

2001-01-01

Photodissociation thresholds of OH from CH sub 3 OH in solid Ne and Ar were determined via photolysis of CH sub 3 OH/Ne and CH sub 3 OH/Ar (1/200) samples in situ at 4 K. The samples were irradiated with VUV synchrotron radiation after dispersion by a Seya-Namioka monochromator. The OH photo-product was detected by means of laser-induced fluorescence technique. The increase of fluorescent intensity of OH was monitored and recorded after the matrix sample was irradiated at different wavelengths for 3-5 min. Photodissociation threshold energies of 7.13+-0.02 eV (174.0+-0.5 nm) and 7.08+-0.04 eV (175.0+-1.0 nm) were measured for OH production of CH sub 3 OH in solid Ne and Ar, respectively.

Laser photodissociation and spectroscopy of mass-separated biomolecular ions

CERN Document Server

Polfer, Nicolas C

2014-01-01

This lecture notes book presents how enhanced structural information of biomolecular ions can be obtained from interaction with photons of specific frequency - laser light. The methods described in the book ""Laser photodissociation and spectroscopy of mass-separated biomolecular ions"" make use of the fact that the discrete energy and fast time scale of photoexcitation can provide more control in ion activation. This activation is the crucial process producing structure-informative product ions that cannot be generated with more conventional heating methods, such as collisional activation. Th

Detection of Indistinct Fe-N Stretching Bands in Iron(V) Nitrides by Photodissociation Spectroscopy

Czech Academy of Sciences Publication Activity Database

Andris, E.; Navrátil, R.; Jašík, J.; Sabenya, G.; Costas, M.; Srnec, Martin; Roithová, J.

2018-01-01

Roč. 24, č. 20 (2018), s. 5078-5081 ISSN 1521-3765 R&D Projects: GA ČR(CZ) GJ15-10279Y Institutional support: RVO:61388955 Keywords : photodissociation spectrochemistry * infrared spectra * DFT Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

State resolved vibrational relaxation modeling for strongly nonequilibrium flows

Science.gov (United States)

Boyd, Iain D.; Josyula, Eswar

2011-05-01

Vibrational relaxation is an important physical process in hypersonic flows. Activation of the vibrational mode affects the fundamental thermodynamic properties and finite rate relaxation can reduce the degree of dissociation of a gas. Low fidelity models of vibrational activation employ a relaxation time to capture the process at a macroscopic level. High fidelity, state-resolved models have been developed for use in continuum gas dynamics simulations based on computational fluid dynamics (CFD). By comparison, such models are not as common for use with the direct simulation Monte Carlo (DSMC) method. In this study, a high fidelity, state-resolved vibrational relaxation model is developed for the DSMC technique. The model is based on the forced harmonic oscillator approach in which multi-quantum transitions may become dominant at high temperature. Results obtained for integrated rate coefficients from the DSMC model are consistent with the corresponding CFD model. Comparison of relaxation results obtained with the high-fidelity DSMC model shows significantly less excitation of upper vibrational levels in comparison to the standard, lower fidelity DSMC vibrational relaxation model. Application of the new DSMC model to a Mach 7 normal shock wave in carbon monoxide provides better agreement with experimental measurements than the standard DSMC relaxation model.

Photodissociation of the acetone cation at 355 nm using the velocity imaging technique

Science.gov (United States)

Jackson, William M.; Xu, Dadong

2000-09-01

Photodissociation of acetone cations, CH3COCH3+, at 355 nm has been studied by means of the ion velocity imaging technique. Acetone cations are produced via direct photoionization of a supersonic beam of acetone at 118 nm generated by frequency tripling the 355 nm laser. Only the acetyl cation, CH3CO+, could be detected as a dissociation product in the time-of-flight mass spectrometer. The acetyl ion signal depends upon the fifth power of the 355 nm laser energy, while the acetone ion signal depends upon the third power. This suggests that the fragment ion is produced via two-photon absorption of 355 nm photons by the acetone cation. The total translational energy distribution and angular distribution of acetyl cation were derived from the 2D images of CH3CO+ for the reaction CH3COCH3++2hν355nm→CH3CO++CH3*. The translational energy distribution suggests that methyl radicals are produced in two electronically excited states, the Rydberg 3s 1 2A1' and the valence 1 2A″ states. The anisotropy parameter β shows that the Rydberg state is formed via a perpendicular excitation and the valence state via a parallel transition.

CO product energy distribution in the photodissociation of methylketene and acrolein at 193 nm

Science.gov (United States)

Fujimoto, G. T.; Umstead, M. E.; Lin, M. C.

1985-04-01

CO product vibrational energy distributions in the photodissociation of the two C3H4O isomers, methylketene (CH3CHCO) and acrolein (CH2CHCHO), at 193 nm have been measured by CO laser resonance absorption. The CO from methylketene was found to be vibrationally excited up to v=7, and from acrolein v=6, with average vibrational energies of 3.4±0.3 and 2.7±0.7 kcal/mol, respectively. The similarities observed in the appearance times and in the vibrational energy content of the CO formed in the two systems support our previous conclusion that in the case of acrolein isomerization to methylketene takes place prior to the dissociation process: CH2CHCHO+hν→CH3CHCO*†→CH3CH+CO†. The CO vibrational energy distributions observed in both systems agree closely with the statistical distribution predicted assuming that ethylidene rather than ethylene is formed in the photodissociation reaction.

Sensitivity of the photodissociation of NO2, NO3, HNO3 and H2O2 to the solar radiation diffused by the ground and by atmospheric particles

International Nuclear Information System (INIS)

Mugnai, A.; Petroncelli, P.; Fiocco, G.

1979-01-01

The diffusion of solar radiation by atmospheric molecules and aerosols and by ground albedo affects the photodissociation rates of atmospheric species relevant to the ozone chemistry. In this paper, a previous investigation on the photodissociation of O 3 is extended to NO 2 , NO 3 , HNO 3 , H 2 O 2 . Because of the different character of the absorption spectra of these species, the behaviour of photodissociation profiles with height and their sensitivity to such factors as ground albedo, aerosol loads, solar zenith angle are somewhat different. The results show that the presence of the aerosols usually enhances the photodissociation in the upper troposphere and in the stratosphere, because of scattering, but tends to reduce it at low heights because of the increased extinction. Enhancements in the photodissociation coefficients are as high as 20 to 40% for low values of the albedo and large aerosol loads such as those obtained after a volcanic eruption. On the other hand, at large values of the albedo, the effect of aerosols is mainly in attenuating the radiation going into and coming from the ground and their presence can lead to reduced photolysis even in the stratosphere. (author)

Photodissociation of anisole and absolute photoionization cross-section of the phenoxy radical.

Science.gov (United States)

Xu, Hong; Pratt, S T

2013-11-21

We have studied the photodissociation dynamics of anisole (C6H5OCH3) at 193 nm and determined the absolute photoionization cross-section of the phenoxy radical at 118.2 nm (10.486 eV) relative to the known cross-section of the methyl radical. Even at this energy, there is extensive fragmentation of the phenoxy radical upon photoionization, which is attributed to ionizing transitions that populate low-lying excited electronic states of the cation. For phenoxy radicals with less than ∼1 eV of internal energy, we find a cross-section for the production of the phenoxy cation of 14.8 ± 3.8 Mb. For radicals with higher internal energy, dissociative ionization is the dominant process, and for internal energies of ∼2.7-3.7 eV, we find a total cross-section (photoionization plus dissociative ionization) of 22.3 ± 4.1 Mb. The results are discussed relative to the recently reported photoionization cross-section of phenol.

Photodissociation spectroscopy of NbnArm complexes

International Nuclear Information System (INIS)

Menezes, W.J.C.; Knickelbein, M.B.

1993-01-01

The optical absorption spectra of niobium clusters containing 7 to 20 atoms have been measured from 336 to 634 nm by way of photodissociation action spectroscopy of the corresponding van der Waals complexes with argon atoms: Nb n Ar m → hν Nb n + m Ar. The clusters in this size range do not display discrete absorption bands characteristic of molecular behavior, but rather absorption cross sections which increase monotonically with decreasing wavelength. This behavior is in qualitative accord with the absorption behavior predicted by the spherical Mie model for small niobium spheres, however, the measured cross sections are 2--5 times larger than predicted over this wavelength range, with the smallest clusters displaying the largest deviations. Interpreted within the classical electrodynamic framework, these observations suggest that the absorption spectra derive oscillator strength from an incipient surface plasmon, redshifted from its predicted resonance frequency in the vacuum ultraviolet

Discrimination of binary coherent states using a homodyne detector and a photon number resolving detector

DEFF Research Database (Denmark)

Wittmann, Christoffer; Andersen, Ulrik Lund; Takeoka, Masahiro

2010-01-01

We investigate quantum measurement strategies capable of discriminating two coherent states probabilistically with significantly smaller error probabilities than can be obtained using nonprobabilistic state discrimination. We apply a postselection strategy to the measurement data of a homodyne...... detector as well as a photon number resolving detector in order to lower the error probability. We compare the two different receivers with an optimal intermediate measurement scheme where the error rate is minimized for a fixed rate of inconclusive results. The photon number resolving (PNR) receiver...

Apparatus for extraction and separation of a preferentially photo-dissociated molecular isotope into positive and negative ions by means of an electric field

International Nuclear Information System (INIS)

Fletcher, J.C.

1978-01-01

Apparatus for the separation and extraction of molecular isotopes is claimed. Molecules of one and the same isotope are preferentially photo-dissociated by a laser and an ultraviolet source, or by multi-photon absorption of laser radiation. The resultant ions are confined with a magnetic field, moved in opposite directions by an electric field, extracted from the photo-dissociation region by means of screening and accelerating grids, and collected in ducts

Testing the effects of message framing, kernel state, and exercise guideline adherence on exercise intentions and resolve.

Science.gov (United States)

de Bruijn, Gert-Jan; Out, Kim; Rhodes, Ryan E

2014-11-01

To study the effects of framed messages on exercise intention and resolve. Two (type of frame: gain or loss) × 2 (type of kernel state: desirable or undesirable outcome) post-test study. Participants were recruited online and questioned about their previous exercise behaviour and their exercise risk perception. After this, they were randomly allocated to one of four messages that were different in terms of positive or negative outcomes (type of frame) and in terms of attained or avoided outcomes (type of kernel state). After reading the message, participants indicated their intention and resolve to engage in sufficient exercise. No effects were found for intention. For resolve, there was a significant interaction between type of frame, type of kernel state, and exercise adherence. Those who did not adhere to the exercise guideline and read the loss-framed message with attained outcomes reported significantly higher resolve than all other participants. This study indicates the relevance of including attained outcomes in message framing exercise interventions as well as a focus on exercise resolve. What is already known on this subject? Message framing is commonly used to increase exercise intentions and behaviour. Meta-analyses do not provide consistent support for this theory. Very little attention has been paid to resolve and message factors on framing effects. What does this study add? Framed messages have an effect on exercise resolve, but not on intention. Loss-framed messages with attained outcomes are most persuasive for those who do not adhere to exercise guidelines. Exercise framing studies should include behavioural resolve next to intention. . © 2014 The British Psychological Society.

Signatures of non-adiabatic dynamics in the fine-structure state distributions of the OH( X ˜ / A ˜ ) products in the B-band photodissociation of H2O

Science.gov (United States)

Zhou, Linsen; Xie, Daiqian; Guo, Hua

2015-03-01

A detailed quantum mechanical characterization of the photodissociation dynamics of H2O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH( X ˜ / A ˜ ) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH( X ˜ , v = 0) exhibit very different characteristics. The A' states, produced mostly via the B ˜ → X ˜ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B ˜ → A ˜ Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH( X ˜ ) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B ˜ → X ˜ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH( A ˜ ) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.

Picosecond real time study of the bimolecular reaction O(3P)+C2H4 and the unimolecular photodissociation of CH3CHO and H2CO

Science.gov (United States)

Abou-Zied, Osama K.; McDonald, J. Douglas

1998-07-01

The bimolecular reaction of O(3P) with ethylene and the unimolecular photodissociation of acetaldehyde and formaldehyde have been studied using a picosecond pump/probe technique. The bimolecular reaction was initiated in a van der Waals dimer precursor, C2H4ṡNO2, and the evolution of the vinoxy radical product monitored by laser-induced fluorescence. The NO2 constituent of the complex was photodissociated at 266 nm. The triplet oxygen atom then attacks a carbon atom of C2H4 to form a triplet diradical (CH2CH2O) which subsequently dissociates to vinoxy (CH2CHO) and H. The rise time of vinoxy radical production was measured to be 217 (+75-25) ps. RRKM theory was applied and a late high exit barrier was invoked in order to fit the measured rise time. The structure and binding energy of the van der Waals complex have been modeled using Lennard-Jones type potentials and the results were compared with other systems. The unimolecular side of the potential energy surfaces of this reaction has been investigated by photodissociating acetaldehyde at the same pump energy of 266 nm. The resulting photoproducts, acetyl radical (CH3CO) and formyl radical (HCO), have been monitored by resonance enhanced multiphoton ionization (REMPI) combined with a time-of-flight mass spectrometer. The similarity in the measured evolution times of both radicals indicates the same photodissociation pathway of the parent molecule. The photodissociation rate of acetaldehyde is estimated from RRKM theory to be very fast (3×1012s-1). The T1←S1 intersystem crossing (ISC) rate is found to be the rate determining step to photodissociation and increases with energy. The REMPI mechanism for the production of CH3CO+ is proposed to be the same as that of HCO+(2+1). The HCO product from the photodissociation of formaldehyde at 266 nm reveals a faster T1←S1 ISC rate than in acetaldehyde.

Photodissociation dynamics of H2O at 111.5 nm by a vacuum ultraviolet free electron laser

Science.gov (United States)

Wang, Heilong; Yu, Yong; Chang, Yao; Su, Shu; Yu, Shengrui; Li, Qinming; Tao, Kai; Ding, Hongli; Yang, Jaiyue; Wang, Guanglei; Che, Li; He, Zhigang; Chen, Zhichao; Wang, Xingan; Zhang, Weiqing; Dai, Dongxu; Wu, Guorong; Yuan, Kaijun; Yang, Xueming

2018-03-01

Photodissociation dynamics of H2O via the F ˜ state at 111.5 nm were investigated using the high resolution H-atom Rydberg "tagging" time-of-flight (TOF) technique, in combination with the tunable vacuum ultraviolet free electron laser at the Dalian Coherent Light Source. The product translational energy distributions and angular distributions in both parallel and perpendicular directions were derived from the recorded TOF spectra. Based on these distributions, the quantum state distributions and angular anisotropy parameters of OH (X) and OH (A) products have been determined. For the OH (A) + H channel, highly rotationally excited OH (A) products have been observed. These products are ascribed to a fast direct dissociation on the B ˜ 1A1 state surface after multi-step internal conversions from the initial excited F ˜ state to the B ˜ state. While for the OH (X) + H channel, very highly rotationally excited OH (X) products with moderate vibrational excitation are revealed and attributed to the dissociation via a nonadiabatic pathway through the well-known two conical intersections between the B ˜ -state and the X ˜ -state surfaces.

Photodissociation and excitation of interstellar molecules

International Nuclear Information System (INIS)

Dishoeck, E.F. van.

1984-01-01

Apart from a rather long introduction containing some elementary astrophysics, quantum chemistry and spectroscopy and an incomplete, historical review of molecular observations, this thesis is divided into three sections. In part A, a rigorous quantum chemical and dynamical study is made of the photodissociation processes in the OH and HCl molecules. In part B, the cross sections obtained in part A are used in various astrophysical problems such as the study of the abundances of the OH and HCl molecules in interstellar clouds, the use of the OH abundance as a measure of the cosmic ray ionization rate, the lifetime of the OH radical in comets and the abundance of OH in the solar photosphere. Part C discusses the excitation of the C 2 molecule under interstellar conditions, its use as a diagnostic probe of the temperature, density and strength of the radiation field in interstellar clouds. Quadrupole moments and oscillator strengths are analyzed. (Auth.)

ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

Science.gov (United States)

Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

2013-11-07

The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

Design of a formaldehyde photodissociation process for carbon and oxygen isotope separation

International Nuclear Information System (INIS)

Stern, R.C.; Scheibner, K.F.

1993-01-01

The current shortage of 18 O has revived interest in using one step UV photodissociation of formaldehyde to enrich 13 C, 17 O and 18 O. The frequency doubled output of the copper laser pumped dye laser system currently in operation at LLNL can be used to drive this dissociation. The authors use a simple kinetics model and their experience with Atomic Vapor Laser Isotope Separation (AVLIS) process design to examine the relative merits of different designs for a formaldehyde photodissociation process. Given values for the molecular photoabsorption cross section, partition function, spectroscopic selectivity, collisional exchange and quenching cross sections (all as parameters), they perform a partial optimization in the space of illuminated area, formaldehyde pressure in each stage, and formaldehyde residence time in each stage. They examine the effect of cascade design (heads and tails staging) on molecule and photon utilization for each of the three isotope separation missions, and look in one case at the system's response to different ratios of laser to formaldehyde costs. Finally, they examine the relative cost of enrichment as a function of isotope and product assay. Emphasis is as much on the process design methodology, which is general, as on the specific application to formaldehyde

Signatures of non-adiabatic dynamics in the fine-structure state distributions of the OH(X{sup ~}/A{sup ~}) products in the B-band photodissociation of H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Zhou, Linsen [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Xie, Daiqian, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Guo, Hua, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

2015-03-28

A detailed quantum mechanical characterization of the photodissociation dynamics of H{sub 2}O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X{sup ~}/A{sup ~}) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X{sup ~}, v = 0) exhibit very different characteristics. The A′ states, produced mostly via the B{sup ~}→X{sup ~} conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B{sup ~}→A{sup ~} Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X{sup ~}) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B{sup ~}→X{sup ~} non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(A{sup ~}) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.

Quantum state-resolved gas/surface reaction dynamics probed by reflection absorption infrared spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Chen Li [Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, Goettingen (Germany); Ueta, Hirokazu; Beck, Rainer D. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Federale de Lausanne (Switzerland); Bisson, Regis [Aix-Marseille Universite, PIIM, CNRS, UMR 7345, 13397 Marseille (France)

2013-05-15

We report the design and characterization of a new molecular-beam/surface-science apparatus for quantum state-resolved studies of gas/surface reaction dynamics combining optical state-specific reactant preparation in a molecular beam by rapid adiabatic passage with detection of surface-bound reaction products by reflection absorption infrared spectroscopy (RAIRS). RAIRS is a non-invasive infrared spectroscopic detection technique that enables online monitoring of the buildup of reaction products on the target surface during reactant deposition by a molecular beam. The product uptake rate obtained by calibrated RAIRS detection yields the coverage dependent state-resolved reaction probability S({theta}). Furthermore, the infrared absorption spectra of the adsorbed products obtained by the RAIRS technique provide structural information, which help to identify nascent reaction products, investigate reaction pathways, and determine branching ratios for different pathways of a chemisorption reaction. Measurements of the dissociative chemisorption of methane on Pt(111) with this new apparatus are presented to illustrate the utility of RAIRS detection for highly detailed studies of chemical reactions at the gas/surface interface.

UV-POSIT: Web-Based Tools for Rapid and Facile Structural Interpretation of Ultraviolet Photodissociation (UVPD) Mass Spectra

Science.gov (United States)

Rosenberg, Jake; Parker, W. Ryan; Cammarata, Michael B.; Brodbelt, Jennifer S.

2018-04-01

UV-POSIT (Ultraviolet Photodissociation Online Structure Interrogation Tools) is a suite of web-based tools designed to facilitate the rapid interpretation of data from native mass spectrometry experiments making use of 193 nm ultraviolet photodissociation (UVPD). The suite includes four separate utilities which assist in the calculation of fragment ion abundances as a function of backbone cleavage sites and sequence position; the localization of charge sites in intact proteins; the calculation of hydrogen elimination propensity for a-type fragment ions; and mass-offset searching of UVPD spectra to identify unknown modifications and assess false positive fragment identifications. UV-POSIT is implemented as a Python/Flask web application hosted at http://uv-posit.cm.utexas.edu. UV-POSIT is available under the MIT license, and the source code is available at https://github.com/jarosenb/UV_POSIT. [Figure not available: see fulltext.

UV-POSIT: Web-Based Tools for Rapid and Facile Structural Interpretation of Ultraviolet Photodissociation (UVPD) Mass Spectra.

Science.gov (United States)

Rosenberg, Jake; Parker, W Ryan; Cammarata, Michael B; Brodbelt, Jennifer S

2018-04-06

UV-POSIT (Ultraviolet Photodissociation Online Structure Interrogation Tools) is a suite of web-based tools designed to facilitate the rapid interpretation of data from native mass spectrometry experiments making use of 193 nm ultraviolet photodissociation (UVPD). The suite includes four separate utilities which assist in the calculation of fragment ion abundances as a function of backbone cleavage sites and sequence position; the localization of charge sites in intact proteins; the calculation of hydrogen elimination propensity for a-type fragment ions; and mass-offset searching of UVPD spectra to identify unknown modifications and assess false positive fragment identifications. UV-POSIT is implemented as a Python/Flask web application hosted at http://uv-posit.cm.utexas.edu . UV-POSIT is available under the MIT license, and the source code is available at https://github.com/jarosenb/UV_POSIT . Graphical Abstract.

UV photodissociation spectroscopy of oxidized undecylenic acid films.

Science.gov (United States)

Gomez, Anthony L; Park, Jiho; Walser, Maggie L; Lin, Ao; Nizkorodov, Sergey A

2006-03-16

Oxidation of thin multilayered films of undecylenic (10-undecenoic) acid by gaseous ozone was investigated using a combination of spectroscopic and mass spectrometric techniques. The UV absorption spectrum of the oxidized undecylenic acid film is significantly red-shifted compared to that of the initial film. Photolysis of the oxidized film in the tropospheric actinic region (lambda > 295 nm) readily produces formaldehyde and formic acid as gas-phase products. Photodissociation action spectra of the oxidized film suggest that organic peroxides are responsible for the observed photochemical activity. The presence of peroxides is confirmed by mass-spectrometric analysis of the oxidized sample and an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is observed. The data strongly imply the importance of photochemistry in aging of atmospheric organic aerosol particles.

Study of photodissociation parameters of carboxyhemoglobin

International Nuclear Information System (INIS)

Kuz'min, V V; Salmin, V V; Provorov, A S; Salmina, A B

2008-01-01

The general properties of photodissociation of carboxyhemoglobin (HbCO) in buffer solutions of whole human blood are studied by the flash photolysis method on a setup with intersecting beams. It is shown that the efficiency of photoinduced dissociation of the HbCO complex virtually linearly depends on the photolytic irradiation intensity for the average power density not exceeding 45 mW cm -2 . The general dissociation of the HbCO complex in native conditions occurs in a narrower range of values of the saturation degree than in model experiments with the hemoglobin solution. The dependence of the pulse photolysis efficiency of HbCO on the photolytic radiation wavelength in the range from 550 to 585 nm has a broad bell shape. The efficiency maximum corresponds to the electronic Q transition (porphyrin π-π* absorption) in HbCO at a wavelength of 570 nm. No dissociation of the complex was observed under given experimental conditions upon irradiation of solutions by photolytic radiation at wavelengths above 585 nm. (laser applications and other topics in quantum electronics)

Isotope effects in gas-phase chemical reactions and photodissociation processes: Overview

International Nuclear Information System (INIS)

Kaye, J.A.

1992-01-01

The origins of isotope effects in equilibrium and non-equilibrium chemical processes are reviewed. In non-equilibrium processes, attention is given to isotope effects in simple bimolecular reactions, symmetry-related reactions, and photodissociation processes. Recent examples of isotope effects in these areas are reviewed. Some indication of other scientific areas for which measurements and/or calculations of isotope effects are used is also given. Examples presented focus on neutral molecule chemistry and in many cases complement examples considered in greater detail in the other chapters of this volume

The effects of nitric oxide cooling and the photodissociation of molecular oxygen on the thermosphere/ionosphere system over the Argentine Islands

Directory of Open Access Journals (Sweden)

G. D. Wells

1997-03-01

Full Text Available In the past the global, fully coupled, time-dependent mathematical model of the Earth's thermosphere/ionosphere/plasmasphere (CTIP has been unable to reproduce accurately observed values of the maximum plasma frequency, foF2, at extreme geophysical locations such as the Argentine Islands during the summer solstice where the ionosphere remains in sunlight throughout the day. This is probably because the seasonal dependence of thermospheric cooling by 5.3 µm nitric oxide has been neglected and the photodissociation of O2 and heating rate calculations have been over-simplified. Now we have included an up-to-date calculation of the solar EUV and UV thermospheric heating rate, coupled with a new calculation of a diurnally varying O2 photodissociation rate, in the model. Seasonally dependent 5.3 µm nitric oxide cooling is also included. With these important improvements, it is found that model values of foF2 are in substantially better agreement with observation. The height of the F2-peak is reduced throughout the day, but remains within acceptable limits of values derived from observation, except at around 0600 h LT. We also carry out two studies of the sensitivity of the upper atmosphere to changes in the magnitude of nitric oxide cooling and photodissociation rates. We find that hmF2 increases with increased heating, whilst foF2 falls. The converse is true for an increase in the cooling rate. Similarly increasing the photodissociation rate increases both hmF2 and foF2. These changes are explained in terms of changes in the neutral temperature, composition and neutral wind.

An atomic perspective of the photodissociation and geminate recombination of triiodide in condensed phases

Energy Technology Data Exchange (ETDEWEB)

Xian, Rui

2016-11-15

The thesis presents progress made towards a thorough understanding of the photodissociation and geminate recombination of triiodide anion (I{sub 3}{sup -}) in solution and solid state using novel time-resolved spectroscopic and structural methods that have matured in the past decade. An isolated I{sub 3}{sup -} has only three degrees of freedom, but in the condensed phase, the case of an open quantum system, its chemistry is transformed because other degrees of freedom from the surroundings (the bath) need to be fully taken into account. This system is a textbook example for understanding dissociation and recombination processes in condensed phases, but unresolved issues about the reaction pathways remain. To probe the issues, firstly, mid-UV pulse shaper-based closed-loop adaptive control as well as open-loop power and chirp control schemes were used in conjunction with single-color pump-probe detection of the yield of the photoproduct diiodide (I{sub 2}{sup -.}) to study the above reaction in ethanol solution. The experiments revealed a strong pump-chirp dependence of the I{sub 2}{sup -.}-yield (as much as 40% change). Subsequently, two possible mechanisms involving additional reaction channels were postulated in order to explain such effect. Secondly, pump-supercontinuum-probe spectroscopy and ultrafast electron diffraction were performed separately on solid state triiodide compound n-(C{sub 4}H{sub 9}){sub 4}NI{sub 3} (TBAT). This system was chosen to provide a well-defined lattice for the bath and to avail atomic resolution of the condensed phase reaction dynamics. In the optical experiment, coherent oscillations were observed within a probe delay of 1 ps that bear strong resemblance to the stretching modes of ground-state I{sub 3}{sup -} and I{sub 2}{sup -.} fragment, which makes it the first to reliably distinguish the two species in a single measurement. In addition, the spectroscopic signature of a novel intermediate, the tetraiodide anion (I{sub 4}{sup

An atomic perspective of the photodissociation and geminate recombination of triiodide in condensed phases

International Nuclear Information System (INIS)

Xian, Rui

2016-11-01

The thesis presents progress made towards a thorough understanding of the photodissociation and geminate recombination of triiodide anion (I_3"-) in solution and solid state using novel time-resolved spectroscopic and structural methods that have matured in the past decade. An isolated I_3"- has only three degrees of freedom, but in the condensed phase, the case of an open quantum system, its chemistry is transformed because other degrees of freedom from the surroundings (the bath) need to be fully taken into account. This system is a textbook example for understanding dissociation and recombination processes in condensed phases, but unresolved issues about the reaction pathways remain. To probe the issues, firstly, mid-UV pulse shaper-based closed-loop adaptive control as well as open-loop power and chirp control schemes were used in conjunction with single-color pump-probe detection of the yield of the photoproduct diiodide (I_2"-".) to study the above reaction in ethanol solution. The experiments revealed a strong pump-chirp dependence of the I_2"-".-yield (as much as 40% change). Subsequently, two possible mechanisms involving additional reaction channels were postulated in order to explain such effect. Secondly, pump-supercontinuum-probe spectroscopy and ultrafast electron diffraction were performed separately on solid state triiodide compound n-(C_4H_9)_4NI_3 (TBAT). This system was chosen to provide a well-defined lattice for the bath and to avail atomic resolution of the condensed phase reaction dynamics. In the optical experiment, coherent oscillations were observed within a probe delay of 1 ps that bear strong resemblance to the stretching modes of ground-state I_3"- and I_2"-". fragment, which makes it the first to reliably distinguish the two species in a single measurement. In addition, the spectroscopic signature of a novel intermediate, the tetraiodide anion (I_4"-".), was identified and its origin is attributed to intermolecular interaction of the

Photodissociation of gaseous CH3COSH at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Observation of three dissociation channels

International Nuclear Information System (INIS)

Hu, En-Lan; Tsai, Po-Yu; Fan, He; Lin, King-Chuen

2013-01-01

Upon one-photon excitation at 248 nm, gaseous CH 3 C(O)SH is dissociated following three pathways with the products of (1) OCS + CH 4 , (2) CH 3 SH + CO, and (3) CH 2 CO + H 2 S that are detected using time-resolved Fourier-transform infrared emission spectroscopy. The excited state 1 (n O , π * CO ) has a radiative lifetime of 249 ± 11 ns long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of collision-induced internal conversion is estimated to be 1.1 × 10 −10 cm 3 molecule −1 s −1 . Among the primary dissociation products, a fraction of the CH 2 CO moiety may undergo further decomposition to CH 2 + CO, of which CH 2 is confirmed by reaction with O 2 producing CO 2 , CO, OH, and H 2 CO. Such a secondary decomposition was not observed previously in the Ar matrix-isolated experiments. The high-resolution spectra of CO are analyzed to determine the ro-vibrational energy deposition of 8.7 ± 0.7 kcal/mol, while the remaining primary products with smaller rotational constants are recognized but cannot be spectrally resolved. The CO fragment detected is mainly ascribed to the primary production. A prior distribution method is applied to predict the vibrational distribution of CO that is consistent with the experimental findings.

Spin-resolved photoemission of surface states of W(110)-(1x1)H

International Nuclear Information System (INIS)

Hochstrasser, M.; Tobin, J.G.; Rotenberg, Eli; Kevan, S.D.

2002-01-01

The surface electronic states of W(110)-(1x1)H have been measured using spin- and angle-resolved photoemission. We directly demonstrate that the surface bands are both split and spin-polarized by the spin-orbit interaction in association with the loss of inversion symmetry near a surface. We observe 100 percent spin polarization of the surface states, with the spins aligned in the plane of the surface and oriented in a circular fashion relative to the S-bar symmetry point. In contrast, no measurable polarization of nearby bulk states is observed

Photodissociation of H2+ by a ruby laser with ion energy analysis of ejected H+

International Nuclear Information System (INIS)

Ozenne, J.B.; Pham, D.; Tadjeddine, M.; Durup, J.

1974-01-01

The kinetic energy released in the photodissociation of H 2 + by a ruby laser beam has been measured. The spectrum of the dissociation kinetic energy of H + +H shows several vibrational levels, and after deconvolution due to the energetic and angular resolution of the apparatus, gives a population of those vibrational levels, close to theoretical population [fr

Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects

DEFF Research Database (Denmark)

Schmidt, Johan Albrecht; Olsen, Jógvan Magnus Haugaard

2014-01-01

The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys.136, 131101 (2012);J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke...

Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

Science.gov (United States)

Haugen, H. K.; Weitz, E.; Leone, S. R.

1985-01-01

Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

Photodissociation of acrylonitrile at 193 nm: A photofragment translational spectroscopy study using synchrotron radiation for product photoionization

International Nuclear Information System (INIS)

Blank, D.A.; Suits, A.G.; Lee, Y.T.; North, S.W.; Hall, G.E.

1998-01-01

We have investigated the photodissociation of acrylonitrile (H 2 CCHCN) at 193 nm using the technique of photofragment translational spectroscopy. The experiments were performed at the Chemical Dynamics Beamline at the Advanced Light Source and used tunable vacuum ultraviolet synchrotron radiation for product photoionization. We have identified four primary dissociation channels including atomic and molecular hydrogen elimination, HCN elimination, and CN elimination. There is significant evidence that all of the dissociation channels occur on the ground electronic surface following internal conversion from the initially optically prepared state. The product translational energy distributions reflect near statistical simple bond rupture for the radical dissociation channels, while substantial recombination barriers mediate the translational energy release for the two molecular elimination channels. Photoionization onsets have provided additional insight into the chemical identities of the products and their internal energy content. copyright 1998 American Institute of Physics

Photodissociation of CH3CHO at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Verification of roaming and triple fragmentation

Science.gov (United States)

Hung, Kai-Chan; Tsai, Po-Yu; Li, Hou-Kuan; Lin, King-Chuen

2014-02-01

By using time-resolved Fourier-transform infrared emission spectroscopy, the HCO fragment dissociated from acetaldehyde (CH3CHO) at 248 nm is found to partially decompose to H and CO. The fragment yields are enhanced by the Ar addition that facilitates the collision-induced internal conversion. The channels to CH2CO + H2 and CH3CO + H are not detected significantly. The rotational population distribution of CO, after removing the Ar collision effect, shows a bimodal feature comprising both low- and high-rotational (J) components, sharing a fraction of 19% and 81%, respectively, for the vibrational state v = 1. The low-J component is ascribed to both roaming pathway and triple fragmentation. They are determined to have a branching ratio of 0.06, respectively, relative to the whole v = 1 population. The CO roaming is accompanied by a highly vibrational population of CH4 that yields a vibrational bimodality.

PHASE-RESOLVED TIMING ANALYSIS OF GRS 1915+105 IN ITS ρ STATE

International Nuclear Information System (INIS)

Yan, Shu-Ping; Wang, Na; Ding, Guo-Qiang; Qu, Jin-Lu

2013-01-01

We made a phase-resolved timing analysis of GRS 1915+105 in its ρ state and obtained detailed ρ cycle evolutions of the frequency, amplitude, and coherence of the low-frequency quasi-periodic oscillation (LFQPO). We combined our timing results with the spectral study by Neilsen et al. to perform an elaborate comparison analysis. Our analyses show that the LFQPO frequency does not scale with the inner disk radius, but it is related to the spectral index, indicating a possible correlation between the LFQPO and the corona. The LFQPO amplitude spectrum and other results are naturally explained by tying the LFQPO to the corona. The similarities of the spectra of variability parameters between the LFQPOs from ρ state and those from more steady states indicate that the LFQPOs of GRS 1915+105 in very different states seem to share the same origin.

PHASE-RESOLVED TIMING ANALYSIS OF GRS 1915+105 IN ITS {rho} STATE

Energy Technology Data Exchange (ETDEWEB)

Yan, Shu-Ping; Wang, Na; Ding, Guo-Qiang [Xinjiang Astronomical Observatory, Chinese Academy of Sciences, 150 Science 1-Street, Urumqi, Xinjiang 830011 (China); Qu, Jin-Lu, E-mail: yanshup@xao.ac.cn, E-mail: na.wang@xao.ac.cn [Key Laboratory for Particle Astrophysics, Institute of High Energy Physics, Chinese Academy of Sciences, 19B Yuquan Road, Beijing 100049 (China)

2013-04-10

We made a phase-resolved timing analysis of GRS 1915+105 in its {rho} state and obtained detailed {rho} cycle evolutions of the frequency, amplitude, and coherence of the low-frequency quasi-periodic oscillation (LFQPO). We combined our timing results with the spectral study by Neilsen et al. to perform an elaborate comparison analysis. Our analyses show that the LFQPO frequency does not scale with the inner disk radius, but it is related to the spectral index, indicating a possible correlation between the LFQPO and the corona. The LFQPO amplitude spectrum and other results are naturally explained by tying the LFQPO to the corona. The similarities of the spectra of variability parameters between the LFQPOs from {rho} state and those from more steady states indicate that the LFQPOs of GRS 1915+105 in very different states seem to share the same origin.

Imaging the Dynamics of CH2BrI Photodissociation in the Near Ultraviolet Region.

Science.gov (United States)

Pan, Changen; Zhang, Yi; Lee, Joseph D; Kidwell, Nathanael M

2018-04-19

The photodissociation dynamics of jet-cooled CH 2 BrI were investigated in the near-ultraviolet (UV) region from 280-310 nm using velocity map imaging. We report the translational and internal energy distributions of the CH 2 Br radical and ground state I ( 2 P 3/2 ) or spin-orbit excited I ( 2 P 1/2 ) fragments determined by velocity map imaging of the ionized iodine fragments following 2 + 1 resonance-enhanced multiphoton ionization of the nascent neutral iodine products. The velocity distributions indicate that most of the available energy is partitioned into the internal energy of the CH 2 Br radical with only modest translational excitation imparted to the cofragments, which is consistent with a simple impulsive model. Furthermore, from extrapolation of the velocity distribution results, the first determination of the C-I bond dissociation energy of CH 2 BrI is presented in this work to be D 0 = 16 790 ± 590 cm -1 . The ion images appear anisotropic, indicative of a prompt dissociation, and the derived anisotropy parameters are consistently positive. Additionally, the angular distributions report on the electronic excited state dynamics, which validate recent works characterizing the electronic states responsible for the first absorption band of CH 2 BrI. In the current work, photolysis of CH 2 BrI on the red edge of the absorption spectrum reveals an additional channel producing I ( 2 P 3/2 ) fragments.

A molecular beam study of the one, two, and three photon photodissociation mechanism of the group VIB (Cr,Mo,W) hexacarbonyls at 248 nm

International Nuclear Information System (INIS)

Venkataraman, B.; Hou, H.; Zhang, Z.; Chen, S.; Bandukwalla, G.; Vernon, M.

1990-01-01

Photodissociation of the group VIB (Cr,Mo,W) hexacarbonyls has been studied at 248 nm using molecular beam photofragment spectroscopy. One, two and three photon processes have been observed. Analysis of the product velocity distributions shows that the photodissociation mechanism consists of sequential CO eliminations with the nth photon channel best described as the single photon photodissociation of the stable products of the n-1st photon channel. The product translational energy distribution for the first CO elimination step is quantitatively similar for all three hexacarbonyls and characteristic of a repulsive translational energy release. The product translational energy distributions of all subsequent CO elimination steps are accurately described by a simple, microcanonical model. Qualitative molecular orbital considerations suggest that the large product translational energy observed in the first CO elimination step results from a repulsive σ interaction between the closed shell CO ligand and an excited molecular orbital which has a significant admixture of metal (n+1)p z , (n+1)s and nd z 2 orbitals. This repulsive interaction is absent in the remaining CO elimination steps because there are vacancies in the coordination shell along the z axis

Photoleucine Survives Backbone Cleavage by Electron Transfer Dissociation. A Near-UV Photodissociation and Infrared Multiphoton Dissociation Action Spectroscopy Study

Czech Academy of Sciences Publication Activity Database

Shaffer, C. J.; Martens, J.; Marek, Aleš; Oomens, J.; Tureček, F.

2016-01-01

Roč. 27, č. 7 (2016), s. 1176-1185 ISSN 1044-0305 Institutional support: RVO:61388963 Keywords : peptide ions * electron transfer dissociation * photoleucine label * near-UV photodissociation * infrared multiphoton dissociation action spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.786, year: 2016

High-harmonic homodyne detection of the ultrafast dissociation of Br2 molecules.

Science.gov (United States)

Wörner, H J; Bertrand, J B; Corkum, P B; Villeneuve, D M

2010-09-03

We report the time-resolved observation of the photodissociation of Br2 using high-harmonic generation (HHG) as a probe. The simultaneous measurement of the high-harmonic and ion yields shows that high harmonics generated by the electronically excited state interfere with harmonics generated by the ground state. The resulting homodyne effect provides a high sensitivity to the excited state dynamics. We present a simple theoretical model that accounts for the main observations. Our experiment paves the way towards the dynamic imaging of molecules using HHG.

Photodissociation dynamics of formyl fluoride (HFCO) at 193 nm: Branching ratios and distributions of kinetic energy

International Nuclear Information System (INIS)

Lee, H.; Wu, C.-Y.; Yang, S.K.; Lee, Y.-P.

2005-01-01

Following photodissociation of formyl fluoride (HFCO) at 193 nm, we detected products with fragmentation translational spectroscopy utilizing a tunable vacuum ultraviolet beam from a synchrotron for ionization. Among three primary dissociation channels observed in this work, the F-elimination channel HFCO→HCO+F dominates, with a branching ratio ∼0.66 and an average release of kinetic energy ∼55 kJ mol -1 ; about 17% of HCO further decomposes to H+CO. The H-elimination channel HFCO→FCO+H has a branching ratio ∼0.28 and an average release of kinetic energy ∼99 kJ mol -1 ; about 21% of FCO further decomposes to F+CO. The F-elimination channel likely proceeds via the S 1 surface whereas the H-elimination channel proceeds via the T 1 surface; both channels exhibit moderate barriers for dissociation. The molecular HF-elimination channel HFCO→HF+CO, correlating with the ground electronic surface, has a branching ratio of only ∼0.06; the average translational release of 93 kJ mol -1 , ∼15% of available energy, implies that the fragments are highly internally excited. Detailed mechanisms of photodissociation are discussed

The role of water-vapour photodissociation on the formation of a deep minimum in mesopause ozone

Directory of Open Access Journals (Sweden)

I. M. Vardavas

1998-02-01

Full Text Available A one-dimensional atmospheric photochemical model with an altitude grid of about 1.5 km was used to examine the structure of the global mean vertical ozone profile and its night-time-to-daytime variation in the upper atmosphere. Two distinct ozone layers are predicted, separated by a sharp drop in the ozone concentration near the mesopause. This naturally occurring mesopause ozone deep minimum is primarily produced by the rapid increase in the destruction of water vapour, and hence increase in HOx, at altitudes between 80 and 85 km, a region where water-vapour photodissociation by ultraviolet radiation of the solar Lyman-alpha line is significant, and where the supply of water vapour is maintained by methane oxidation even for very dry conditions at the tropospheric-stratospheric exchange region. The model indicates that the depth of the mesopause ozone minimum is limited by the efficiency with which inactive molecular hydrogen is produced, either by the conversion of atomic hydrogen to molecular hydrogen via one of the reaction channels of H with HO2, or by Lyman-alpha photodissociation of water vapour via the channel that leads to the production of molecular hydrogen. The ozone concentration rapidly recovers above 85 km due to the rapid increase in O produced by the photodissociation of O2 by absorption of ultraviolet solar radiation in the Schumann-Runge bands and continuum. Above 90 km, there is a decrease in ozone due to photolysis as the production of ozone through the three-body recombination of O2 and O becomes slower with decreasing pressure. The model also predicts two peaks in the night-time/daytime ozone ratio, one near 75 km and the other near 110 km, plus a strong peak in the night-time/daytime ratio of OH near 110 km. Recent observational evidence supports the predictions of the model.Key words. Atmospheric composition and structure · Middle atmosphere · Thermosphere · Transmission and scattering of radiation

Quantum state engineering, purification, and number-resolved photon detection with high-finesse optical cavities

DEFF Research Database (Denmark)

Nielsen, Anne E. B.; Muschik, Christine A.; Giedke, Geza

2010-01-01

We propose and analyze a multifunctional setup consisting of high-finesse optical cavities, beam splitters, and phase shifters. The basic scheme projects arbitrary photonic two-mode input states onto the subspace spanned by the product of Fock states |n>|n> with n=0,1,2,.... This protocol does no...... is especially attractive as a generalization to many modes allows for distribution and purification of entanglement in networks. In an alternative working mode, the setup allows for quantum nondemolition number resolved photodetection in the optical domain....

The photodissociation of 8B and the solar neutrino problem

International Nuclear Information System (INIS)

Bertulani, C.A.

1995-01-01

The extraction of the photodissociation cross sections of 8 B from Coulomb dissociation experiments is investigated. A careful study is done on the contributions of the E1, E2 and M1 multipolarities to the breakup. A comparison with the data of a recent experiment is performed. It is shown that the extraction of the radiative capture cross sections 7 Be(p, γ) 8 B which are relevant for the solar neutrino problem is not affected appreciably by Coulomb reacceleration. A non-perturbative model is used for the purpose. Emphasis is put on the perspectives for future experiments which are planned at the University of Notre Dame, RIKEN (Japan), and GSI (Germany). An analysis of the total yields of ''photon-point'' processes in inelastic electron scattering is also done. (orig.)

Temperature dependence of the photodissociation of CO2 from high vibrational levels: 205-230 nm imaging studies of CO(X1Σ+) and O(3P, 1D) products

Science.gov (United States)

Sutradhar, S.; Samanta, B. R.; Samanta, A. K.; Reisler, H.

2017-07-01

The 205-230 nm photodissociation of vibrationally excited CO2 at temperatures up to 1800 K was studied using Resonance Enhanced Multiphoton Ionization (REMPI) and time-sliced Velocity Map Imaging (VMI). CO2 molecules seeded in He were heated in an SiC tube attached to a pulsed valve and supersonically expanded to create a molecular beam of rotationally cooled but vibrationally hot CO2. Photodissociation was observed from vibrationally excited CO2 with internal energies up to about 20 000 cm-1, and CO(X1Σ+), O(3P), and O(1D) products were detected by REMPI. The large enhancement in the absorption cross section with increasing CO2 vibrational excitation made this investigation feasible. The internal energies of heated CO2 molecules that absorbed 230 nm radiation were estimated from the kinetic energy release (KER) distributions of CO(X1Σ+) products in v″ = 0. At 230 nm, CO2 needs to have at least 4000 cm-1 of rovibrational energy to absorb the UV radiation and produce CO(X1Σ+) + O(3P). CO2 internal energies in excess of 16 000 cm-1 were confirmed by observing O(1D) products. It is likely that initial absorption from levels with high bending excitation accesses both the A1B2 and B1A2 states, explaining the nearly isotropic angular distributions of the products. CO(X1Σ+) product internal energies were estimated from REMPI spectroscopy, and the KER distributions of the CO(X1Σ+), O(3P), and O(1D) products were obtained by VMI. The CO product internal energy distributions change with increasing CO2 temperature, suggesting that more than one dynamical pathway is involved when the internal energy of CO2 (and the corresponding available energy) increases. The KER distributions of O(1D) and O(3P) show broad internal energy distributions in the CO(X1Σ+) cofragment, extending up to the maximum allowed by energy but peaking at low KER values. Although not all the observations can be explained at this time, with the aid of available theoretical studies of CO2 VUV

Photodissociation of 1,2-dibromoethylene at 248 nm: Br2 molecular elimination probed by cavity ring-down absorption spectroscopy.

Science.gov (United States)

Chang, Yuan-Pin; Lee, Ping-Chen; Lin, King-Chuen; Huang, C H; Sun, B J; Chang, A H H

2008-06-02

The Br2 elimination channel is probed for 1,2-C2H2Br2 in the B(3)Pi(+)ou-X(1)Sigma(+)g transition upon irradiation at 248 nm by using cavity ring-down absorption spectroscopy (CRDS). The nascent vibrational population ratio of Br2(v=1)/Br2(v=0) is obtained to be 0.7+/-0.2, thus indicating that the Br2 fragment is produced in hot vibrational states. The obtained Br2 products are anticipated to result primarily from photodissociation of the ground-state cis isomer via four-center elimination or from cis/trans isomers via three-center elimination, each mechanism involving a transition state that has a Br-Br distance much larger than that of ground state Br2. According to ab initio potential energy calculations, the pathways that lead to Br2 elimination may proceed either through the electronic ground state by internal conversion or through the triplet state by intersystem crossing. Temperature-dependence measurements are examined, thereby supporting the pathway that involves internal conversion--which was excluded previously by using product translational spectroscopy (PTS). The quantum yield for the Br2 elimination reaction is determined to be 0.120.1, being substantially contributed by the ground-state Br2 product. The discrepancy of this value from that (of 0.2) obtained by PTS may rise from the lack of measurements in probing the triplet-state Br2 product.

Diabatic potential-optimized discrete variable representation: application to photodissociation process of the CO molecule

International Nuclear Information System (INIS)

Bitencourt, Ana Carla P; Prudente, Frederico V; Vianna, Jose David M

2007-01-01

We propose a new numerically optimized discrete variable representation using eigenstates of diabatic Hamiltonians. This procedure provides an efficient method to solve non-adiabatic coupling problems since the generated basis sets take into account information on the diabatic potentials. The method is applied to the B 1 Σ + - D' 1 Σ + Rydberg-valence predissociation interaction in the CO molecule. Here we give an account of the discrete variable representation and present the procedure for the calculation of its optimized version, which we apply to obtain the total photodissociation cross sections of the CO molecule

A single-column particle-resolved model for simulating the vertical distribution of aerosol mixing state: WRF-PartMC-MOSAIC-SCM v1.0

Science.gov (United States)

Curtis, Jeffrey H.; Riemer, Nicole; West, Matthew

2017-11-01

The PartMC-MOSAIC particle-resolved aerosol model was previously developed to predict the aerosol mixing state as it evolves in the atmosphere. However, the modeling framework was limited to a zero-dimensional box model approach without resolving spatial gradients in aerosol concentrations. This paper presents the development of stochastic particle methods to simulate turbulent diffusion and dry deposition of aerosol particles in a vertical column within the planetary boundary layer. The new model, WRF-PartMC-MOSAIC-SCM, resolves the vertical distribution of aerosol mixing state. We verified the new algorithms with analytical solutions for idealized test cases and illustrate the capabilities with results from a 2-day urban scenario that shows the evolution of black carbon mixing state in a vertical column.

Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

Science.gov (United States)

Chang, Xue-Ping; Fang, Qiu; Cui, Ganglong

2014-10-01

Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S0, T1, and S1 states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S1 system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S1/S0 conical intersection funnels the S1 to S0 state. Then, some trajectories continue completing the decarboxylation reaction in the S0 state; the remaining trajectories via a reverse hydrogen transfer return to the S0 minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S1 -T1 energy gap and a large S1/T1 spin-orbit coupling, an efficient S1 → T1 intersystem crossing process happens again near this S1/S0 conical intersection. When decaying to T1 state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S1 system first decays to the T1 state via an S1 → T1 intersystem crossing; then, the T1 system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T1 decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T1 ESIPT process, there also exists a comparable Norrish type I reaction in the T1 state, which forms the ground-state products of CH3CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S1-T1 and S1-S0 energy gaps, effecting an S1/T1/S0 three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate.

Science.gov (United States)

Tsai, Po-Yu; Chao, Meng-Hsuan; Kasai, Toshio; Lin, King-Chuen; Lombardi, Andrea; Palazzetti, Federico; Aquilanti, Vincenzo

2014-02-21

The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.

Picosecond dynamics of reactions in the liquid phase: studies of iodine photodissociation and development of new laser techniques

International Nuclear Information System (INIS)

Berg, M.A.

1985-09-01

Iodine photodissociation and recombination was studied as a model for processes common to chemical reaction in the liquid phase. Picosecond transient absorption measurements from 1000 to 295 nm were used to monitor the dynamics in a variety of solvents. Most of the atoms which undergo geminate recombination were found to do so in less than or equal to 15 ps, in agreement with the results of existing molecular dynamics simulations. Vibrational relaxation times vary from approx.15 ps near the middle of the ground state well to approx.150 ps for complete relaxation to v = 0. The prediction of strong resonant vibrational energy transfer to chlorinated methane solvents was not supported, but some evidence for this mechanism was found for alkane solvents. Current theory is unable to explain the large variation (65 to 2700 ps) of the excited A'-state lifetime in various solvents. The 10-Hz amplified, synchronously-pumped dye laser which was used in these studies is described and characterized. SERS (Stimulated Electronic Raman Scattering) and difference frequency mixing were used in the generation of the infrared and far-infrared, respectively. 54 refs., 38 figs., 3 tabs

Schrödinger–Langevin equation with quantum trajectories for photodissociation dynamics

Energy Technology Data Exchange (ETDEWEB)

Chou, Chia-Chun, E-mail: ccchou@mx.nthu.edu.tw

2017-02-15

The Schrödinger–Langevin equation is integrated to study the wave packet dynamics of quantum systems subject to frictional effects by propagating an ensemble of quantum trajectories. The equations of motion for the complex action and quantum trajectories are derived from the Schrödinger–Langevin equation. The moving least squares approach is used to evaluate the spatial derivatives of the complex action required for the integration of the equations of motion. Computational results are presented and analyzed for the evolution of a free Gaussian wave packet, a two-dimensional barrier model, and the photodissociation dynamics of NOCl. The absorption spectrum of NOCl obtained from the Schrödinger–Langevin equation displays a redshift when frictional effects increase. This computational result agrees qualitatively with the experimental results in the solution-phase photochemistry of NOCl.

Photodissociative Cross-Linking of Non-covalent Peptide-Peptide Ion Complexes in the Gas Phase

Science.gov (United States)

Nguyen, Huong T. H.; Andrikopoulos, Prokopis C.; Rulíšek, Lubomír; Shaffer, Christopher J.; Tureček, František

2018-05-01

We report a gas-phase UV photodissociation study investigating non-covalent interactions between neutral hydrophobic pentapeptides and peptide ions incorporating a diazirine-tagged photoleucine residue. Phenylalanine (Phe) and proline (Pro) were chosen as the conformation-affecting residues that were incorporated into a small library of neutral pentapeptides. Gas-phase ion-molecule complexes of these peptides with photo-labeled pentapeptides were subjected to photodissociation. Selective photocleavage of the diazirine ring at 355 nm formed short-lived carbene intermediates that underwent cross-linking by insertion into H-X bonds of the target peptide. The cross-link positions were established from collision-induced dissociation tandem mass spectra (CID-MS3) providing sequence information on the covalent adducts. Effects of the amino acid residue (Pro or Phe) and its position in the target peptide sequence were evaluated. For proline-containing peptides, interactions resulting in covalent cross-links in these complexes became more prominent as proline was moved towards the C-terminus of the target peptide sequence. The photocross-linking yields of phenylalanine-containing peptides depended on the position of both phenylalanine and photoleucine. Density functional theory calculations were used to assign structures of low-energy conformers of the (GLPMG + GLL*LK + H)+ complex. Born-Oppenheimer molecular dynamics trajectory calculations were used to capture the thermal motion in the complexes within 100 ps and determine close contacts between the incipient carbene and the H-X bonds in the target peptide. This provided atomic-level resolution of potential cross-links that aided spectra interpretation and was in agreement with experimental data. [Figure not available: see fulltext.

Sigma*-mediated electronic relaxation in 200nm photoexcited ammonia and heteroaromatics

Directory of Open Access Journals (Sweden)

Evans N. L.

2013-03-01

Full Text Available Time–resolved photoelectron spectra of ammonia display combination bands of the umbrella and stretching modes associated with the N–H coordinate of σ* relaxation. Time–resolved photodissociation studies determine timescales <200fs. Similar σ* photochemistry is found in heteroaromatics

Photodissociation of H2+ by intense chirped pulses - beyond the effect of pulse duration and peak power

International Nuclear Information System (INIS)

Lev, U; Prabhudesai, V; Natan, A; Bruner, B; Diner, A; Heber, O; Strasser, D; Schwalm, D; Silberberg, Y; Zajfman, D; Ben-Itzhak, I; Hua, J J; Esry, B D

2009-01-01

H 2 + photodissociation, induced by intense short laser pulses, was measured by a full 3D imaging system. We have conducted a series of experiments, in which we systematically changed the linear chirp, using a pulse shaper, and observed the kinetic energy release spectra(KER). Distinct differences in the KER spectra are observed both in peak positions and angular distribution for laser pulses with similar duration and intensity but opposite chirp sign.

Steady state and time-resolved spectroscopic investigations on the photoreactions involved within the electronically excited electron acceptor 9-cyanoanthracene in presence of benzotriazole and benzimidazole donors

International Nuclear Information System (INIS)

Bhattacharya, Sudeshna; Bardhan, Munmun; Ganguly, Tapan

2010-01-01

The electrochemical, 'steady-state' and 'time-resolved' spectroscopic investigations were made on the well-known electron acceptor 9-cyanoanthracene (CNA) when interacted with the electron donors benzotriazole (BZT) and benzimidazole (BMI) molecules. Though electrochemical measurements indicate the thermodynamical possibility of occurrences of photoinduced electron transfer reactions within these reacting systems in the lowest excited singlet state (S 1 ) of the acceptor CNA but the steady-state and time-resolved measurements clearly demonstrate only the triplet-initiated charge separation reactions. It was reported earlier that in the cases of disubstituted indole molecules the occurrences of photoinduced electron transfer reactions were apparent both in the excited singlet and triplet states of the acceptor 9-cyanoanthracene, but the similarly structured present donor molecules benzotriazole (and benzimidazole) behave differently from indoles. The weak ground state complex formations within the presently studied reacting systems appear to be responsible for the observed static quenching phenomena as evidenced from the time-resolved fluorescence studies. Time-resolved spectroscopic investigations demonstrate the formation of the ground state of the reacting components (donor and acceptor) through recombination of triplet ion-pairs via formations of contact neutral radical produced by H-abstraction mechanism.

Testing the effects of message framing, kernel state, and exercise guideline adherence on exercise intentions and resolve

NARCIS (Netherlands)

de Bruijn, G.J.; Out, K.; Rhodes, R.E.

2014-01-01

Objectives To study the effects of framed messages on exercise intention and resolve. Design Two (type of frame: gain or loss) × 2 (type of kernel state: desirable or undesirable outcome) post-test study. Methods Participants were recruited online and questioned about their previous exercise

Determination of electronic states in crystalline semiconductors and metals by angle-resolved photoemission

International Nuclear Information System (INIS)

Mills, K.A.

1979-08-01

An important part of the theoretical description of the solid state is band structure, which relies on the existence of dispersion relations connecting the electronic energy and wavevector in materials with translational symmetry. These relations determine the electronic behavior of such materials. The elaboration of accurate band structures, therefore, is of considerable fundamental and practical importance. Angle-resolved photoemission (ARP) spectroscopy provides the only presently available method for the detailed experimental investigation of band structures. This work is concerned with its application to both semiconducting and metallic single crystals

Isomer-specific detection in the UV photodissociation of the propargyl radical by chirped-pulse mm-wave spectroscopy in a pulsed quasi-uniform flow.

Science.gov (United States)

Broderick, Bernadette M; Suas-David, Nicolas; Dias, Nureshan; Suits, Arthur G

2018-02-21

Isomer-specific detection and product branching fractions in the UV photodissociation of the propargyl radical is achieved through the use of chirped-pulse Fourier-transform mm-wave spectroscopy in a pulsed quasi-uniform flow (CPUF). Propargyl radicals are produced in the 193 nm photodissociation of 1,2-butadiene. Absorption of a second photon leads to H atom elimination giving three possible C 3 H 2 isomers: singlets cyclopropenylidene (c-C 3 H 2 ) and propadienylidene (l-C 3 H 2 ), and triplet propargylene ( 3 HCCCH). The singlet products and their appearance kinetics in the flow are directly determined by rotational spectroscopy, but due to the negligible dipole moment of propargylene, it is not directly monitored. However, we exploit the time-dependent kinetics of H-atom catalyzed isomerization to infer the branching to propargylene as well. We obtain the overall branching among H loss channels to be 2.9% (+1.1/-0.5) l-C 3 H 2 + H, 16.8% (+3.2/-1.3) c-C 3 H 2 + H, and 80.2 (+1.8/-4.2) 3 HCCCH + H. Our findings are qualitatively consistent with earlier RRKM calculations in that the major channel in the photodissociation of the propargyl radical at 193 nm is to 3 HCCCH + H; however, a greater contribution to the energetically most favorable isomer, c-C 3 H 2 + H is observed in this work. We do not detect the predicted HCCC + H 2 channel, but place an upper bound on its yield of 1%.

The steady-state and time-resolved photophysical properties of a dimeric indium phthalocyanine complex

International Nuclear Information System (INIS)

Chen Yu; Araki, Yasuyuki; Dini, Danilo; Liu Ying; Ito, Osamu; Fujitsuka, Mamoru

2006-01-01

The steady-state and time-resolved photophysical properties and some molecular orbital calculation results of a dimeric indium phthalocyanine complex with an indium-indium bond, i.e., [tBu 4 PcIn] 2 .2tmed, have been described. The results regarding triplet excited state lifetimes can be ascribed to strong intramolecular interactions existing only in the excited state of this dimer because no significant difference in the absorption spectra of the tBu 4 PcInCl monomer and the [tBu 4 PcIn] 2 .2tmed dimer is observed, suggesting that no ground-state interaction can be assessed. The deactivation processes of the excited singlet state of [tBu 4 PcIn] 2 .2tmed are apparently faster than that of μ-oxo-bridged PcIn dimer [tBu 4 PcIn] 2 O. Molecular orbital calculation on the PcIn dimer shows no node between two indium atoms was found in the HOMO - 2 of the PcIn-InPc dimer, suggesting that bonding electrons distribute between two indium atoms

Photodissociation dynamics of the iodide-uracil (I{sup −}U) complex

Energy Technology Data Exchange (ETDEWEB)

Li, Wei-Li; Kunin, Alice [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Matthews, Edward; Yoshikawa, Naruo; Dessent, Caroline E. H., E-mail: dneumark@berkeley.edu, E-mail: caroline.dessent@york.ac.uk [Department of Chemistry, University of York, Heslington, York YO10 5DD (United Kingdom); Neumark, Daniel M., E-mail: dneumark@berkeley.edu, E-mail: caroline.dessent@york.ac.uk [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

2016-07-28

Photofragment action spectroscopy and femtosecond time-resolved photoelectron imaging are utilized to probe the dissociation channels in iodide-uracil (I{sup −} ⋅ U) binary clusters upon photoexcitation. The photofragment action spectra show strong I{sup −} and weak [U—H]{sup −} ion signal upon photoexcitation. The action spectra show two bands for I{sup −} and [U—H]{sup −} production peaking around 4.0 and 4.8 eV. Time-resolved experiments measured the rate of I{sup −} production resulting from excitation of the two bands. At 4.03 eV and 4.72 eV, the photoelectron signal from I{sup −} exhibits rise times of 86 ± 7 ps and 36 ± 3 ps, respectively. Electronic structure calculations indicate that the lower energy band, which encompasses the vertical detachment energy (4.11 eV) of I{sup −}U, corresponds to excitation of a dipole-bound state of the complex, while the higher energy band is primarily a π–π{sup ∗} excitation on the uracil moiety. Although the nature of the two excited states is very different, the long lifetimes for I{sup −} production suggest that this channel results from internal conversion to the I{sup −} ⋅ U ground state followed by evaporation of I{sup −}. This hypothesis was tested by comparing the dissociation rates to Rice-Ramsperger-Kassel-Marcus calculations.

Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

Energy Technology Data Exchange (ETDEWEB)

Chang, Xue-Ping; Fang, Qiu, E-mail: fangqiu917@bnu.edu.cn; Cui, Ganglong, E-mail: ganglong.cui@bnu.edu.cn [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)

2014-10-21

Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S{sub 0}, T{sub 1}, and S{sub 1} states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S{sub 1} system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S{sub 1}/S{sub 0} conical intersection funnels the S{sub 1} to S{sub 0} state. Then, some trajectories continue completing the decarboxylation reaction in the S{sub 0} state; the remaining trajectories via a reverse hydrogen transfer return to the S{sub 0} minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S{sub 1} −T{sub 1} energy gap and a large S{sub 1}/T{sub 1} spin-orbit coupling, an efficient S{sub 1} → T{sub 1} intersystem crossing process happens again near this S{sub 1}/S{sub 0} conical intersection. When decaying to T{sub 1} state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S{sub 1} system first decays to the T{sub 1} state via an S{sub 1} → T{sub 1} intersystem crossing; then, the T{sub 1} system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T{sub 1} decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T{sub 1} ESIPT process, there also exists a comparable Norrish type I reaction in the T{sub 1} state, which forms the ground-state products of CH{sub 3}CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S{sub 1}-T{sub 1} and S{sub 1}-S{sub 0} energy gaps, effecting an S{sub 1}/T{sub 1}/S{sub 0} three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

Photodissociation of acetone from 266 to 312 nm: Dynamics of CH3 + CH3CO channels on the S0 and T1 states

Science.gov (United States)

Lee, Kin Long Kelvin; Nauta, Klaas; Kable, Scott H.

2017-01-01

The photodissociation dynamics of acetone (CH3)2CO, cooled in a molecular beam, have been explored over the wavelength range 266-312 nm. Nascent CH3 fragments were detected by resonance-enhanced multiphoton ionization, followed by mass-selected ion imaging. For photolysis at λ = 306 nm, the image shows a sharp ring, which, when converted to a translational energy distribution, reveals a narrow Gaussian peak with a maximum at 90% of the available energy. As the photolysis energy is increased, the distribution slowly broadens and shifts to higher recoil translational energy. The fraction of available energy in translation energy decreases in favour of internal energy of the CH3CO fragment. These observations are consistent with a dynamical model in which the energy of the exit channel barrier on the T1 surface evolves mostly into relative translational energy. Energy in excess of the barrier is partitioned statistically into all degrees of freedom. No evidence was found for any other dynamical pathway producing CH3 fragments, including reaction on S0 or S1, for dissociation between 306 and 266 nm. For λ > 306 nm, a diffuse, slow recoil component to the image appears. The translational energy distribution for this component is fit well by a statistical prior distribution of energy. We attribute this component to dissociation on the S0, ground state surface; to our knowledge, this is the first direct observation of this channel. The appearance of S0 dynamics and the disappearance of the T1 component are consistent with previously inferred barrier height on T1 for the production of CH3CO + CH3. The possible atmospheric implications of our findings are discussed.

Time-resolved cathodoluminescence microscopy with sub-nanosecond beam blanking for direct evaluation of the local density of states

NARCIS (Netherlands)

Moerland, R.J.; Weppelman, I.G.C.; Garming, M.W.H.; Kruit, P.; Hoogenboom, J.P.

2016-01-01

We show cathodoluminescence-based time-resolved electron beam spectroscopy in order to directly probe the spontaneous emission decay rate that is modified by the local density of states in a nanoscale environment. In contrast to dedicated laser-triggered electron-microscopy setups, we use commercial

Photodissociation of van der Waals clusters of isoprene with oxygen, C{sub 5}H{sub 8}-O{sub 2}, in the wavelength range 213-277 nm

Energy Technology Data Exchange (ETDEWEB)

Vidma, Konstantin V.; Frederix, Pim W. J. M.; Parker, David H. [Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 ED Nijmegen (Netherlands); Baklanov, Alexey V. [Institute of Chemical Kinetics and Combustion, Institutskaja Street 3, Novosibirsk 630090 (Russian Federation) and Novosibirsk State University, Pirogova street 2, Novosibirsk 630090 (Russian Federation)

2012-08-07

The speed and angular distribution of O atoms arising from the photofragmentation of C{sub 5}H{sub 8}-O{sub 2}, the isoprene-oxygen van der Waals complex, in the wavelength region of 213-277 nm has been studied with the use of a two-color dissociation-probe method and the velocity map imaging technique. Dramatic enhancement in the O atoms photo-generation cross section in comparison with the photodissociation of individual O{sub 2} molecules has been observed. Velocity map images of these 'enhanced' O atoms consisted of five channels, different in their kinetic energy, angular distribution, and wavelength dependence. Three channels are deduced to be due to the one-quantum excitation of the C{sub 5}H{sub 8}-O{sub 2} complex into the perturbed Herzberg III state ({sup 3}{Delta}{sub u}) of O{sub 2}. This excitation results in the prompt dissociation of the complex giving rise to products C{sub 5}H{sub 8}+O+O when the energy of exciting quantum is higher than the complex photodissociation threshold, which is found to be 41740 {+-} 200 cm{sup -1} (239.6{+-}1.2 nm). This last threshold corresponds to the photodissociation giving rise to an unexcited isoprene molecule. The second channel, with threshold shifted to the blue by 1480 {+-} 280 cm{sup -1}, corresponds to dissociation with formation of rovibrationally excited isoprene. A third channel was observed at wavelengths up to 243 nm with excitation below the upper photodissociation threshold. This channel is attributed to dissociation with the formation of a bound O atom C{sub 5}H{sub 8}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}O + O and/or to dissociation of O{sub 2} with borrowing of the lacking energy from incompletely cooled complex internal degrees of freedom C{sub 5}H{sub 8}{sup *}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}{sup *}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}+ O + O. The kinetic energy of the O atoms arising in two other

Influence of light-induced conical intersection on the photodissociation dynamics of D2(+) starting from individual vibrational levels.

Science.gov (United States)

Halász, Gábor J; Csehi, András; Vibók, Ágnes; Cederbaum, Lorenz S

2014-12-26

Previous works have shown that dressing of diatomic molecules by standing or by running laser waves gives rise to the appearance of so-called light-induced conical intersections (LICIs). Because of the strong nonadiabatic couplings, the existence of such LICIs may significantly change the dynamical properties of a molecular system. In our former paper (J. Phys. Chem. A 2013, 117, 8528), the photodissociation dynamics of the D(2)(+) molecule were studied in the LICI framework starting the initial vibrational nuclear wave packet from the superposition of all the vibrational states initially produced by ionizing D(2). The present work complements our previous investigation by letting the initial nuclear wave packets start from different individual vibrational levels of D(2)(+), in particular, above the energy of the LICI. The kinetic energy release spectra, the total dissociation probabilities, and the angular distributions of the photofragments are calculated and discussed. An interesting phenomenon has been found in the spectra of the photofragments. Applying the light-induced adiabatic picture supported by LICI, explanations are given for the unexpected structure of the spectra.

Investigations on the photoreactions of phenothiazine and phenoxazine in presence of 9-cyanoanthracene by using steady state and time resolved spectroscopic techniques.

Science.gov (United States)

Bardhan, Munmun; Mandal, Paulami; Tzeng, Wen-Bih; Ganguly, Tapan

2010-09-01

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).

Photodissociation of water. II. Wave packet calculations for the photofragmentation of H2O and D2O in the B˜ band

Science.gov (United States)

van Harrevelt, Rob; van Hemert, Marc C.

2000-04-01

A complete three-dimensional quantum mechanical description of the photodissociation of water in the B˜ band, starting from its rotational ground state, is presented. In order to include B˜-X˜ vibronic coupling and the B˜-Ã Renner-Teller coupling, diabatic electronic states have been constructed from adiabatic electronic states and matrix elements of the electronic angular momentum operators, following the procedure developed by A. J. Dobbyn and P. J. Knowles [Mol. Phys. 91, 1107 (1997)], using the ab initio results discussed in the preceding paper. The dynamics is studied using wave packet methods, and the evolution of the time-dependent wave function is discussed in detail. Results for the H2O and D2O absorption spectra, OH(A)/OH(X) and OD(A)/OD(X) branching ratios, and rovibrational distributions of the OH and OD fragments are presented and compared with available experimental data. The present theoretical results agree at least qualitatively with the experiments. The calculations show that the absorption spectrum and the product state distributions are strongly influenced by long-lived resonances on the adiabatic B˜ state. It is also shown that molecular rotation plays an important role in the photofragmentation process, due to both the Renner-Teller B˜-X˜ mixing, and the strong effect of out-of-plane molecular rotations (K>0) on the dynamics at near linear HOH and HHO geometries.

A new crossed molecular beam apparatus using time-sliced ion velocity imaging technique

International Nuclear Information System (INIS)

Wu Guorong; Zhang Weiqing; Pan Huilin; Shuai Quan; Jiang Bo; Dai Dongxu; Yang Xueming

2008-01-01

A new crossed molecular beam apparatus has been constructed for investigating polyatomic chemical reactions using the time-sliced ion velocity map imaging technique. A unique design is adopted for one of the two beam sources and allows us to set up the molecular beam source either horizontally or vertically. This can be conveniently used to produce versatile atomic or radical beams from photodissociation and as well as electric discharge. Intensive H-atom beam source with high speed ratio was produced by photodissociation of the HI molecule and was reacted with the CD 4 molecule. Vibrational-state resolved HD product distribution was measured by detecting the CD 3 product. Preliminary results were also reported on the F+SiH 4 reaction using the discharged F atom beam. These results demonstrate that this new instrument is a powerful tool for investigating chemical dynamics of polyatomic reactions.

Resolving discrete pulsar spin-down states with current and future instrumentation

Science.gov (United States)

Shaw, B.; Stappers, B. W.; Weltevrede, P.

2018-04-01

An understanding of pulsar timing noise offers the potential to improve the timing precision of a large number of pulsars as well as facilitating our understanding of pulsar magnetospheres. For some sources, timing noise is attributable to a pulsar switching between two different spin-down rates (\\dot{ν }). Such transitions may be common but difficult to resolve using current techniques. In this work, we use simulations of \\dot{ν }-variable pulsars to investigate the likelihood of resolving individual \\dot{ν } transitions. We inject step changes in the value of \\dot{ν } with a wide range of amplitudes and switching time-scales. We then attempt to redetect these transitions using standard pulsar timing techniques. The pulse arrival-time precision and the observing cadence are varied. Limits on \\dot{ν } detectability based on the effects such transitions have on the timing residuals are derived. With the typical cadences and timing precision of current timing programmes, we find that we are insensitive to a large region of Δ \\dot{ν } parameter space that encompasses small, short time-scale switches. We find, where the rotation and emission states are correlated, that using changes to the pulse shape to estimate \\dot{ν } transition epochs can improve detectability in certain scenarios. The effects of cadence on Δ \\dot{ν } detectability are discussed, and we make comparisons with a known population of intermittent and mode-switching pulsars. We conclude that for short time-scale, small switches, cadence should not be compromised when new generations of ultra-sensitive radio telescopes are online.

Photodissociation of H{sub 2}{sup +} by intense chirped pulses - beyond the effect of pulse duration and peak power

Energy Technology Data Exchange (ETDEWEB)

Lev, U; Prabhudesai, V; Natan, A; Bruner, B; Diner, A; Heber, O; Strasser, D; Schwalm, D; Silberberg, Y; Zajfman, D [Faculty of Physics, Weizmann Institute of Science, Rehovot 76100 (Israel); Ben-Itzhak, I; Hua, J J; Esry, B D, E-mail: uri.lev@Weizmann.ac.i [Department of Physics, Kansas State University, Manhattan, KS 66506 (United States)

2009-11-01

H{sub 2}{sup +} photodissociation, induced by intense short laser pulses, was measured by a full 3D imaging system. We have conducted a series of experiments, in which we systematically changed the linear chirp, using a pulse shaper, and observed the kinetic energy release spectra(KER). Distinct differences in the KER spectra are observed both in peak positions and angular distribution for laser pulses with similar duration and intensity but opposite chirp sign.

Model of comet comae. II. Effects of solar photodissociative ionization

International Nuclear Information System (INIS)

Huebner, W.F.; Giguere, P.T.

1980-01-01

Improvements to our computer model of coma plotochemistry are described. These include an expansion of the chemical reactions network and new rate constants that have been measured only recently. Photolytic reactions of additional molecules are incorporated, and photolytic branching ratios are treated in far greater detail than in our previous work. A total of 25 photodissociative ionization (PDI) reactions are now considered (as compared to only 3 PDI reactions previously). Solar PDI of the mother molecule CO 2 is shown to compete effectively with photoionization of CO in the production of observed CO + . The CO + density peak predicted by our improved model, for COP 2 or CO mother molecules, is deep in the inner coma, in better agreement with observation than our old CO 2 model. However, neither CO 2 nor CO mother molecule calculations reproduce the CO + /H 2 O + ratio observed in comet Kohoutek. PDI products of CO 2 , CO, CH 4 , and NH 3 mother molecules fuel a complex chemistry scheme, producing inner coma abundances of CN, C 2 , and C 3 much greater than previously calculated

Properties of Highly Rotationally Excited H2 in Photodissociation Regions

Science.gov (United States)

Cummings, Sally Jane; Wan, Yier; Stancil, Phillip C.; Yang, Benhui H.; Zhang, Ziwei

2018-06-01

H2 is the dominant molecular species in the vast majority of interstellar environments and it plays a crucial role as a radiative coolant. In photodissociation regions, it is one of the primary emitters in the near to mid-infrared which are due to lines originating from highly excited rotational levels. However, collisional data for rotational levels j>10 are sparse, particularly for H2-H2 collisions. Utilizing new calculations for para-H2 and ortho-H2 collisional rate coefficients with H2 for j as high as 30, we investigate the effects of the new results in standard PDR models with the spectral simulation package Cloudy. We also perform Cloudy models of the Orion Bar and use Radex to explore rotational line ratio diagnostics. The resulting dataset of H2 collisional data should find wide application to other molecular environments. This work was support by Hubble Space Telescope grant HST-AR-13899.001-A and NASA grants NNX15AI61G and NNX16AF09G.

Chloroacetone photodissociation at 193 nm and the subsequent dynamics of the CH3C(O)CH2 radical—an intermediate formed in the OH + allene reaction en route to CH3 + ketene

Science.gov (United States)

Alligood, Bridget W.; FitzPatrick, Benjamin L.; Szpunar, David E.; Butler, Laurie J.

2011-02-01

We use a combination of crossed laser-molecular beam experiments and velocity map imaging experiments to investigate the primary photofission channels of chloroacetone at 193 nm; we also probe the dissociation dynamics of the nascent CH3C(O)CH2 radicals formed from C-Cl bond fission. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence another photodissociation channel of the precursor, C-C bond fission to produce CH3CO and CH2Cl. The CH3C(O)CH2 radical formed from C-Cl bond fission is one of the intermediates in the OH + allene reaction en route to CH3 + ketene. The 193 nm photodissociation laser allows us to produce these CH3C(O)CH2 radicals with enough internal energy to span the dissociation barrier leading to the CH3 + ketene asymptote. Therefore, some of the vibrationally excited CH3C(O)CH2 radicals undergo subsequent dissociation to CH3 + ketene products; we are able to measure the velocities of these products using both the imaging and scattering apparatuses. The results rule out the presence of a significant contribution from a C-C bond photofission channel that produces CH3 and COCH2Cl fragments. The CH3C(O)CH2 radicals are formed with a considerable amount of energy partitioned into rotation; we use an impulsive model to explicitly characterize the internal energy distribution. The data are better fit by using the C-Cl bond fission transition state on the S1 surface of chloroacetone as the geometry at which the impulsive force acts, not the Franck-Condon geometry. Our data suggest that, even under atmospheric conditions, the reaction of OH with allene could produce a small branching to CH3 + ketene products, rather than solely producing inelastically stabilized adducts. This additional channel offers a different pathway for the OH-initiated oxidation of such unsaturated volatile organic compounds, those containing a C=C=C moiety, than is currently included in atmospheric models.

Vibrational frequencies and dephasing times in excited electronic states by femtosecond time-resolved four-wave mixing

Science.gov (United States)

Joo, Taiha; Albrecht, A. C.

1993-06-01

Time-resolved degenerate four-wave mixing (TRDFWM) for an electronically resonant system in a phase-matching configuration that measures population decay is reported. Because the spectral width of input light exceeds the vibrational Bohr frequency of a strong Raman active mode, the vibrational coherence produces strong oscillations in the TRDFWM signal together with the usual population decay from the excited electronic state. The data are analyzed in terms of a four-level system: ground and excited electronic states each split by a vibrational quantum of a Raman active mode. Absolute frequencies and their dephasing times of the vibrational modes at ≈590 cm -1 are obtained for the excited as well as the ground electronic state. The vibrational dephasing rate in the excited electronic state is about an order of magnitude faster than that in the ground state, the origin of which is speculated upon.

Space resolved x-ray diffraction measurements of the supercooled state of polymers

International Nuclear Information System (INIS)

Asano, Tsutomu; Yoshida, Shinya; Nishida, Akira; Mina, M.F.

2002-01-01

In order to measure an ordering process of polymers, the supercooled state near the crystallizing surface was observed by a space resolved X-ray diffraction method at Photon Factory (PF). Using temperature slope crystallization, low density polyethylene and even-number paraffins were examined during crystallization from the melt state. The results indicate that polyethylene shows a sharp b-axis orientation where the lamellar normal and crystalline c-axis are perpendicular to the temperature slope. The crystalline lamellae are well-developed with lamellar thickness of 180 A. The supercooled melt state just above the crystallizing plane shows some diffraction in the small angle region without any crystalline reflection in the wide angle. This fact suggests that a long-range ordering (lamellar structure) appears prior to the short-range one (crystalline structure). The in-situ crystallizing surface was observed by an optical microscope connected to a TV system. The crystallizing surface of even-number paraffins moves to upwards in the temperature slope. In-situ X-ray measurements at PF revealed that the crystalline c-axis and lamellar normal of the even number paraffins are parallel to the temperature slope. From these results, the crystalline ordering and the surface movement of even number paraffins are explained using special nucleation mechanism including a screw dislocation. (author)

Dissociation dynamics of CH3I in electric spark induced breakdown revealed by time-resolved laser induced breakdown spectroscopy

International Nuclear Information System (INIS)

Wang, Yang; Liu, Wei-long; Song, Yun-fei; Duo, Li-ping; Liu, Yu-qiang; Yang, Yan-qiang

2015-01-01

Highlights: • Emission of electric spark dissociation of CH 3 I is similar to its fs LIBS. • We use fs laser induced breakdown as a simulation for electric spark dissociation. • The I 2 molecule formation is directly observed in the time-resolved LIBS. • Bimolecular collision of I ∗ and CH 3 I is responsible for the formation of I 2 . - Abstract: The electric discharge spark dissociation of gas CH 3 I is found to be similar to its femtosecond laser photodissociation. The almost identical spectra of the two processes show that their initial ionization conditions are very similar. The initial ionization followed by molecular fragmentation is proposed as the dissociation mechanism, in which the characteristic emissions of I + , CH 3 , CH 2 , CH, H, and I 2 are identified as the dissociation products. The emission band of 505 nm I 2 is clearly observed in the time-resolved laser induced breakdown spectroscopy (LIBS). The dynamic curve indicates that I 2 ∗ molecules are formed after the delay time of ∼4.7 ns. The formation of I 2 ∗ molecule results from the bimolecular collision of the highly excited iodine atom I ∗ ( 4 P) and CH 3 I molecule. This dynamical information can help understand the process of electric discharge spark dissociation of CH 3 I

The influence of internal degrees of freedom on the unimolecular decay of the molecule-cluster compound Au8+CH3OH

Science.gov (United States)

Vogel, M.; Hansen, K.; Herlert, A.; Schweikhard, L.; Walther, C.

2002-06-01

Time-resolved photodissociation measurements of the sequential reaction Au8+CH3OH→Au8+→Au7+ and the direct reaction Au8+→Au7+ have been performed for several excitation energies. The production rates and yields of the final state Au7+ in the sequential process are strongly influenced by the excitation energy deposited into the evaporated methanol molecule during the initial fragmentation step. Both the rate constants and yields can be fitted with a single parameter, the cluster-methanol binding energy.

Three-dimensional photodissociation in strong laser fields: Memory-kernel effective-mode expansion

International Nuclear Information System (INIS)

Li Xuan; Thanopulos, Ioannis; Shapiro, Moshe

2011-01-01

We introduce a method for the efficient computation of non-Markovian quantum dynamics for strong (and time-dependent) system-bath interactions. The past history of the system dynamics is incorporated by expanding the memory kernel in exponential functions thereby transforming in an exact fashion the non-Markovian integrodifferential equations into a (larger) set of ''effective modes'' differential equations (EMDE). We have devised a method which easily diagonalizes the EMDE, thereby allowing for the efficient construction of an adiabatic basis and the fast propagation of the EMDE in time. We have applied this method to three-dimensional photodissociation of the H 2 + molecule by strong laser fields. Our calculations properly include resonance-Raman scattering via the continuum, resulting in extensive rotational and vibrational excitations. The calculated final kinetic and angular distribution of the photofragments are in overall excellent agreement with experiments, both when transform-limited pulses and when chirped pulses are used.

Photon number projection using non-number-resolving detectors

International Nuclear Information System (INIS)

Rohde, Peter P; Webb, James G; Huntington, Elanor H; Ralph, Timothy C

2007-01-01

Number-resolving photo-detection is necessary for many quantum optics experiments, especially in the application of entangled state preparation. Several schemes have been proposed for approximating number-resolving photo-detection using non-number-resolving detectors. Such techniques include multi-port detection and time-division multiplexing. We provide a detailed analysis and comparison of different number-resolving detection schemes, with a view to creating a useful reference for experimentalists. We show that the ideal architecture for projective measurements is a function of the detector's dark count and efficiency parameters. We also describe a process for selecting an appropriate topology given actual experimental component parameters

Geometric phase effects in the coherent control of the branching ratio of photodissociation products of phenol

International Nuclear Information System (INIS)

Abe, Mayumi; Ohtsuki, Yukiyoshi; Fujimura, Yuichi; Lan, Zhenggang; Domcke, Wolfgang

2006-01-01

Optimal control simulation is used to examine the control mechanisms in the photodissociation of phenol within a two-dimensional, three-electronic-state model with two conical intersections. This model has two channels for H-atom elimination, which correspond to the 2 π and 2 σ states of the phenoxyl radical. The optimal pulse that enhances 2 σ dissociation initially generates a wave packet on the S 1 potential-energy surface of phenol. This wave packet is bifurcated at the S 2 -S 1 conical intersection into two components with opposite phases because of the geometric phase effect. The destructive interference caused by the geometric phase effect reduces the population around the S 1 -S 0 conical intersection, which in turn suppresses nonadiabatic transitions and thus enhances dissociation to the 2 σ limit. The optimal pulse that enhances S 0 dissociation, on the other hand, creates a wave packet on the S 2 potential-energy surface of phenol via an intensity borrowing mechanism, thus avoiding geometric phase effects at the S 2 -S 1 conical intersection. This wave packet hits the S 1 -S 0 conical intersection directly, resulting in preferred dissociation to the 2 π limit. The optimal pulse that initially prepares the wave packet on the S 1 potential-energy surface (PES) has a higher carrier frequency than the pulse that prepares the wave packet on the S 2 PES. This counterintuitive effect is explained by the energy-level structure and the S 2 -S 1 vibronic coupling mechanism

High-Resolution Photoionization, Photoelectron and Photodissociation Studies. Determination of Accurate Energetic and Spectroscopic Database for Combustion Radicals and Molecules

Energy Technology Data Exchange (ETDEWEB)

Ng, Cheuk-Yiu [Univ. of California, Davis, CA (United States)

2016-04-25

The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

Photodissociation comprehensive study of OH- on alkali halides and their interaction with colour centers

International Nuclear Information System (INIS)

Gomes, L.

1985-01-01

This work shows that the OH - defect induces changes in the electronics processes of the alkali halides such as in radiation damage and optical cycles of colour centers. Two cases were considered: with the presence of an OH - ion in the (1) excited state and (2) in the ground state; 1) the comprehensive study of resonant OH - photodissociation in several hosts showed that deep traps (for electrons) can be produced from the OH - dissociation. These traps can be effective for the capture of electrons produced in the radiation damage of the lattice as well as for trapping electrons from ionized color centers. It was observed a second channel (new) for the de-excitation of the (OH - )* molecule in KI and RbI. This effect can be effective only when the lattice around the molecule holds a large enough interstitial space. This new mechanism is responsible for the strong production at LNT of F centers and OH 0 molecules at the expenses of OH - defects. Considering the complete investigation of the full cycle it was proposed a phenomenological model that would explain the observed behaviour when one covers a wide variation of lattice parameters (KCl -> RbI); 2) It was verified that the OH - ion present in the lattice induces strong changes in the de-excitation processes of electronic defects with a spread out wave function (like F centers). A change in the reorientation behaviour of excited F 2 and F + 2 centers was also verified. Two main effects should be mentioned: A) The induced de-excitation is very fast and non-radiative on F centers. B) Another type of system investigated (F 2 and F + 2 ) has shown an intense increase of the speed of reorientation of the F 2 and F + 2 excited centers. (autor) [pt

Photodissociation dynamics of CO2 at 157.6 nm by photofragment-translational spectroscopy

International Nuclear Information System (INIS)

Stolow, A.; Lee, Y.T.

1993-01-01

The photodissociation of CO 2 at 157 nm was studied by the photofragment-translational spectroscopy technique. Product time-of-flight spectra were recorded and center-of-mass translational energy distributions were determined. Two electronic channels were observed---one forming O( 1 D) and the other O( 3 P). With previously determined anisotropy parameters of β=2 for the O( 3 P) channel and β=0 for the O( 1 D) channel, an electronic branching ratio of 6%±2%O( 3 P) was obtained, consistent with previous results. The translational energy distribution for the CO(v)+O( 3 P) channel was very broad (over 30 kcal/mol) and appeared to peak near CO(v=0). The value of β=2 for the O( 3 P) channel was confirmed by comparing Doppler profiles, derived from our measured translational energy distribution, with previously measured Doppler profiles. This suggests that the O( 3 P) channel arises from a direct transition to an excited triplet state. The O( 1 D) channel had a structured time-of-flight which related to rovibrational distributions of the CO product. The influence of the excitation of the CO 2 (ν 2 ) bending mode was investigated and shown to have a small but not negligible contribution. Based upon a comparison of our data with a previous vacuum-ultraviolet (VUV) laser induced fluorescence study, we obtain as our best estimate of the vibrational branching ratio, CO(v=0)/CO(v=1)=1.9, for the CO(v)+O( 1 D) channel

State-Resolved Metal Nanoparticle Dynamics Viewed through the Combined Lenses of Ultrafast and Magneto-optical Spectroscopies.

Science.gov (United States)

Zhao, Tian; Herbert, Patrick J; Zheng, Hongjun; Knappenberger, Kenneth L

2018-05-08

Electronic carrier dynamics play pivotal roles in the functional properties of nanomaterials. For colloidal metals, the mechanisms and influences of these dynamics are structure dependent. The coherent carrier dynamics of collective plasmon modes for nanoparticles (approximately 2 nm and larger) determine optical amplification factors that are important to applied spectroscopy techniques. In the nanocluster domain (sub-2 nm), carrier coupling to vibrational modes affects photoluminescence yields. The performance of photocatalytic materials featuring both nanoparticles and nanoclusters also depends on the relaxation dynamics of nonequilibrium charge carriers. The challenges for developing comprehensive descriptions of carrier dynamics spanning both domains are multifold. Plasmon coherences are short-lived, persisting for only tens of femtoseconds. Nanoclusters exhibit discrete carrier dynamics that can persist for microseconds in some cases. On this time scale, many state-dependent processes, including vibrational relaxation, charge transfer, and spin conversion, affect carrier dynamics in ways that are nonscalable but, rather, structure specific. Hence, state-resolved spectroscopy methods are needed for understanding carrier dynamics in the nanocluster domain. Based on these considerations, a detailed understanding of structure-dependent carrier dynamics across length scales requires an appropriate combination of spectroscopic methods. Plasmon mode-specific dynamics can be obtained through ultrafast correlated light and electron microscopy (UCLEM), which pairs interferometric nonlinear optical (INLO) with electron imaging methods. INLO yields nanostructure spectral resonance responses, which capture the system's homogeneous line width and coherence dynamics. State-resolved nanocluster dynamics can be obtained by pairing ultrafast with magnetic-optical spectroscopy methods. In particular, variable-temperature variable-field (VTVH) spectroscopies allow quantification

Relevance of the law of international organisations in resolving ...

African Journals Online (AJOL)

structures to resolve disputes between states. Uncertainty remains, however, on the availability of effective structures within the system to resolve disputes between international organisations. It is important to note that international organisations were, prior to 1945, not considered subjects of international law so as to be ...

Highly-resolved modeling of personal transportation energy consumption in the United States

International Nuclear Information System (INIS)

Muratori, Matteo; Moran, Michael J.; Serra, Emmanuele; Rizzoni, Giorgio

2013-01-01

This paper centers on the estimation of the total primary energy consumption for personal transportation in the United States, to include gasoline and/or electricity consumption, depending on vehicle type. The bottom-up sector-based estimation method introduced here contributes to a computational tool under development at The Ohio State University for assisting decision making in energy policy, pricing, and investment. In order to simulate highly-resolved consumption profiles three main modeling steps are needed: modeling the behavior of drivers, generating realistic driving profiles, and simulating energy consumption of different kinds of vehicles. The modeling proposed allows for evaluating the impact of plug-in electric vehicles on the electric grid – especially at the distribution level. It can serve as a tool to compare different vehicle types and assist policy-makers in estimating their impact on primary energy consumption and the role transportation can play to reduce oil dependency. - Highlights: • Modeling primary energy consumption for personal transportation in the United States. • Behavior of drivers has been simulated in order to establish when driving events occur and the length of each event. • Realistic driving profiles for each driving event are generated using a stochastic model. • The model allows for comparing the initial cost of different vehicles and their expected energy-use operating cost. • Evaluation of the impact of PEVs on the electric grid – especially at the distribution level – can be performed

Relative quantum yield of I-asterisk(2P1/2) in the tunable laser UV photodissociation of i-C3F7I and n-C3F7I - Effect of temperature and exciplex emission

Science.gov (United States)

Smedley, J. E.; Leone, S. R.

1983-01-01

Wavelength-specific relative quantum yields of metastable I from pulsed laser photodissociation of i-C3F7I and n-C3F7I in the range 265-336 nm are determined by measuring the time-resolved infrared emission from the atomic I(P-2(1/2) P-2(3/2) transition. It is shown that although this yield appears to be unity from 265 to 298 nm, it decreases dramatically at longer wavelengths. Values are also reported for the enhancement of emission from metastable I due to exciplex formation at several temperatures. The exciplex formation emission increases linearly with parent gas pressure, but decreases with increasing temperature. Absorption spectra of i- and n-C3F7I between 303 and 497 K are presented, and the effect of temperature on the quantum yields at selected wavelengths greater than 300 nm, where increasing the temperature enhances the absorption considerably, are given. The results are discussed in regard to the development of solar-pumped iodine lasers.

Time-resolved spectroscopy in synchrotron radiation

International Nuclear Information System (INIS)

Rehn, V.; Stanford Univ., CA

1980-01-01

Synchrotron radiation (SR) from large-diameter storage rings has intrinsic time structure which facilitates time-resolved measurements form milliseconds to picoseconds and possibly below. The scientific importance of time-resolved measurements is steadily increasing as more and better techniques are discovered and applied to a wider variety of scientific problems. This paper presents a discussion of the importance of various parameters of the SR facility in providing for time-resolved spectroscopy experiments, including the role of beam-line optical design parameters. Special emphasis is placed on the requirements of extremely fast time-resolved experiments with which the effects of atomic vibrational or relaxation motion may be studied. Before discussing the state-of-the-art timing experiments, we review several types of time-resolved measurements which have now become routine: nanosecond-range fluorescence decay times, time-resolved emission and excitation spectroscopies, and various time-of-flight applications. These techniques all depend on a short SR pulse length and a long interpulse period, such as is provided by a large-diameter ring operating in a single-bunch mode. In most cases, the pulse shape and even the stability of the pulse shape is relatively unimportant as long as the pulse length is smaller than the risetime of the detection apparatus, typically 1 to 2 ns. For time resolution smaller than 1 ns, the requirements on the pulse shape become more stringent. (orig./FKS)

Investigations on the interactions of aurintricarboxylic acid with bovine serum albumin: Steady state/time resolved spectroscopic and docking studies.

Science.gov (United States)

Bardhan, Munmun; Chowdhury, Joydeep; Ganguly, Tapan

2011-01-10

In this paper, the nature of the interactions between bovine serum albumin (BSA) and aurintricarboxylic acid (ATA) has been investigated by measuring steady state and time-resolved fluorescence, circular dichroism (CD), FT-IR and fluorescence anisotropy in protein environment under physiological conditions. From the analysis of the steady state and time-resolved fluorescence quenching of BSA in aqueous solution in presence of ATA it has been inferred that the nature of the quenching originates from the combined effect of static and dynamic modes. From the determination of the thermodynamic parameters obtained from temperature-dependent changes in K(b) (binding constant) it was apparent that the combined effect of hydrophobic association and electrostatic attraction is responsible for the interaction of ATA with BSA. The effect of ATA on the conformation of BSA has been examined by analyzing CD spectrum. Though the observed results demonstrate some conformational changes in BSA in presence of ATA but the secondary structure of BSA, predominantly of α-helix, is found to retain its identity. Molecular docking of ATA with BSA also indicates that ATA docks through hydrophobic interaction. Copyright © 2010 Elsevier B.V. All rights reserved.

Relationship between time-resolved and non-time-resolved Beer-Lambert law in turbid media.

Science.gov (United States)

Nomura, Y; Hazeki, O; Tamura, M

1997-06-01

The time-resolved Beer-Lambert law proposed for oxygen monitoring using pulsed light was extended to the non-time-resolved case in a scattered medium such as living tissues with continuous illumination. The time-resolved Beer-Lambert law was valid for the phantom model and living tissues in the visible and near-infrared regions. The absolute concentration and oxygen saturation of haemoglobin in rat brain and thigh muscle could be determined. The temporal profile of rat brain was reproduced by Monte Carlo simulation. When the temporal profiles of rat brain under different oxygenation states were integrated with time, the absorbance difference was linearly related to changes in the absorption coefficient. When the simulated profiles were integrated, there was a linear relationship within the absorption coefficient which was predicted for fractional inspiratory oxygen concentration from 10 to 100% and, in the case beyond the range of the absorption coefficient, the deviation from linearity was slight. We concluded that an optical pathlength which is independent of changes in the absorption coefficient is a good approximation for near-infrared oxygen monitoring.

Femtosecond Time-Resolved Resonance-Enhanced CARS of Gaseous Iodine at Room Temperature

International Nuclear Information System (INIS)

He Ping; Fan Rong-Wei; Xia Yuan-Qin; Yu Xin; Chen De-Ying; Yao Yong

2011-01-01

Time-resolved resonance-enhanced coherent anti-Stokes Raman scattering (CARS) is applied to investigate molecular dynamics in gaseous iodine. 40 fs laser pulses are applied to create and monitor the high vibrational states of iodine at room temperature (corresponding to a vapor pressure as low as about 35 Pa) by femtosecond time-resolved CARS. Depending on the time delay between the probe pulse and the pump/Stokes pulse pairs, the high vibrational states both on the electronically ground states and the excited states can be detected as oscillations in the CARS transient signal. It is proved that the femtosecond time-resolved CARS technique is a promising candidate for investigating the molecular dynamics of a low concentration system and can be applied to environmental and atmospheric monitoring measurements. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

On the resolvents methods in quantum perturbation calculations

International Nuclear Information System (INIS)

Burzynski, A.

1979-01-01

This paper gives a systematic review of resolvent methods in quantum perturbation calculations. The case of discrete spectrum of hamiltonian is considered specially (in the literature this is the fewest considered case). The topics of calculations of quantum transitions by using of the resolvent formalism, quantum transitions between states from particular subspaces, the shifts of energy levels, are shown. The main ideas of stationary perturbation theory developed by Lippmann and Schwinger are considered too. (author)

The analysis of time-resolved optically stimulated luminescence: I. Theoretical considerations

International Nuclear Information System (INIS)

Chithambo, M L

2007-01-01

This is the first of two linked papers on the analysis of time-resolved optically stimulated luminescence. This paper focusses on a theoretical basis of analytical methods and on methods for interpretation of time-resolved luminescence spectra and calculation of luminescence throughput. Using a comparative analysis of the principal features of time-resolved luminescence and relevant analogues from steady state optical stimulation, formulae for configuring a measurement system for optimum performance are presented. We also examine the possible use of stretched-exponential functions for analysis of time-resolved optically stimulated luminescence spectra

Accurate Quantum Wave Packet Study of the Deep Well D+ + HD Reaction: Product Ro-vibrational State-Resolved Integral and Differential Cross Sections.

Science.gov (United States)

He, Haixiang; Zhu, Weimin; Su, Wenli; Dong, Lihui; Li, Bin

2018-03-08

The H + + H 2 reaction and its isotopic variants as the simplest triatomic ion-molecule reactive system have been attracting much interests, however there are few studies on the titled reaction at state-to-state level until recent years. In this work, accurate state-to-state quantum dynamics studies of the titled reaction have been carried out by a reactant Jacobi coordinate-based time-dependent wave packet approach on diabatic potential energy surfaces constructed by Kamisaka et al. Product ro-vibrational state-resolved information has been calculated for collision energies up to 0.2 eV with maximal total angular momentum J = 40. The necessity of including all K-component for accounting the Coriolis coupling for the reaction has been illuminated. Competitions between the two product channels, (D + + HD' → D' + + HD and D + + HD' → H + + DD') were investigated. Total integral cross sections suggest that resonances enhance the reactivity of channel D + + HD'→ H + + DD', however, resonances depress the reactivity of the another channel D + + HD' → D' + + HD. The structures of the differential cross sections are complicated and depend strongly on collision energies of the two channels and also on the product rotational states. All of the product ro-vibrational state-resolved differential cross sections for this reaction do not exhibit rigorous backward-forward symmetry which may indicate that the lifetimes of the intermediate resonance complexes should not be that long. The dynamical observables of this deuterated isotopic reaction are quite different from the reaction of H + + H 2 → H 2 + H + reported previously.

The elementary steps of the photodissociation and recombination reactions of iodine molecules enclosed in cages and channels of zeolite crystals: A femtosecond time-resolved study of the geometry effect

International Nuclear Information System (INIS)

Flachenecker, G.; Materny, A.

2004-01-01

We present femtosecond time-resolved pump-probe experiments on iodine molecules enclosed into well-defined cages and channels of different crystalline SiO 2 modifications of zeolites. The new experimental results obtained from iodine in TON (Silica-ZSM-22), FER (Silica-Ferrierit), and MFI (Silicalit-1) porosils are compared with data published earlier on the iodine/DDR (Decadodecasil 3R) porosil system [Flachenecker et al., Phys. Chem. Chem. Phys. 5, 865 (2003)]. A summary of all findings is given. The processes analyzed by means of the ultrafast spectroscopy are the vibrational relaxation as well as the dissociation and recombination reactions, which are caused by the interaction of the photo-excited iodine molecules with the cavity walls of the porosils. A clear dependence of the observed dynamics on the geometry of the surrounding lattice structure can be seen. These measurements are supported by temperature-dependent experiments. Making use of a theoretical model which is based on the classical Langevin equation, an analysis of the geometry-reaction relation is performed. The Brownian dynamics simulations show that in contrast to the vibrational relaxation the predissociation dynamics are independent of the frequency of collisions with the surroundings. From the results obtained in the different surroundings, we conclude that mainly local fields are responsible for the crossing from the bound B state to the repulsive a/a ' states of the iodine molecules

Pressure and temperature-dependent quantum yields for the photodissociation of acetone between 279 and 327.5 nm

Science.gov (United States)

Blitz, M. A.; Heard, D. E.; Pilling, M. J.; Arnold, S. R.; Chipperfield, M. P.

2004-03-01

The photodissociation of acetone has been studied over the wavelength (λ) range 279-327.5 nm as a function of temperature (T) and pressure (p) using a spectroscopic method to monitor the acetyl (CH3CO) radical fragment. Above 310 nm the quantum yield (QY) is substantially smaller than previous measurements, and decreases with T. The QYs for production of CH3CO + CH3 and CH3 + CH3 + CO have been parameterised as a function of λ, p and T and used to calculate the altitude dependence of the photolysis frequency. In the upper troposphere (UT) the acetone photolysis lifetime is a factor of 2.5-10 longer, dependent upon latitude and season, than if the previously recommended QYs are used.

Photodissociation of NaK: Ab initio spin-orbit interaction of the Na (32S) and K (42Pj) manifold

International Nuclear Information System (INIS)

Manaa, M.R.

1999-01-01

The relevant interstate b 3 II, A 1 Σ + , c 3 Σ + , and B 1 II spin-orbit induced matrix elements, arising from the Ma (3 2 S) K (4 2 P j ) manifold are treated within the full microscopic Breit-Pauli approximation based on ab initio configuration interaction (CI) wave functions. The determination of these couplings as a function of the internuclear distance of NaK should permit a full treatment of the fine-structure branching ratio K*(4 2 P 1/2 (D 1 ))/Kasterisk(4 2 P 3/2 (D 2 )) in manifold-meditated photodissociation and in the treatment of interstate perturbations

Gas phase structures and charge localization in small aluminum oxide anions: Infrared photodissociation spectroscopy and electronic structure calculations

Energy Technology Data Exchange (ETDEWEB)

Song, Xiaowei; Fagiani, Matias R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany); Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig (Germany); Gewinner, Sandy; Schöllkopf, Wieland [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany); Asmis, Knut R., E-mail: knut.asmis@uni-leipzig.de, E-mail: js@chemie.hu-berlin.de [Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig (Germany); Bischoff, Florian A.; Berger, Fabian; Sauer, Joachim, E-mail: knut.asmis@uni-leipzig.de, E-mail: js@chemie.hu-berlin.de [Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, D-10099 Berlin (Germany)

2016-06-28

We use cryogenic ion trap vibrational spectroscopy in combination with quantum chemical calculations to study the structure of mono- and dialuminum oxide anions. The infrared photodissociation spectra of D{sub 2}-tagged AlO{sub 1-4}{sup −} and Al{sub 2}O{sub 3-6}{sup −} are measured in the region from 400 to 1200 cm{sup −1}. Structures are assigned based on a comparison to simulated harmonic and anharmonic IR spectra derived from electronic structure calculations. The monoaluminum anions contain an even number of electrons and exhibit an electronic closed-shell ground state. The Al{sub 2}O{sub 3-6}{sup −} anions are oxygen-centered radicals. As a result of a delicate balance between localization and delocalization of the unpaired electron, only the BHLYP functional is able to qualitatively describe the observed IR spectra of all species with the exception of AlO{sub 3}{sup −}. Terminal Al–O stretching modes are found between 1140 and 960 cm{sup −1}. Superoxo and peroxo stretching modes are found at higher (1120-1010 cm{sup −1}) and lower energies (850-570 cm{sup −1}), respectively. Four modes in-between 910 and 530 cm{sup −1} represent the IR fingerprint of the common structural motif of dialuminum oxide anions, an asymmetric four-member Al–(O){sub 2}–Al ring.

Top-Down Hydrogen-Deuterium Exchange Analysis of Protein Structures Using Ultraviolet Photodissociation.

Science.gov (United States)

Brodie, Nicholas I; Huguet, Romain; Zhang, Terry; Viner, Rosa; Zabrouskov, Vlad; Pan, Jingxi; Petrotchenko, Evgeniy V; Borchers, Christoph H

2018-03-06

Top-down hydrogen-deuterium exchange (HDX) analysis using electron capture or transfer dissociation Fourier transform mass spectrometry (FTMS) is a powerful method for the analysis of secondary structure of proteins in solution. The resolution of the method is a function of the degree of fragmentation of backbone bonds in the proteins. While fragmentation is usually extensive near the N- and C-termini, electron capture (ECD) or electron transfer dissociation (ETD) fragmentation methods sometimes lack good coverage of certain regions of the protein, most often in the middle of the sequence. Ultraviolet photodissociation (UVPD) is a recently developed fast-fragmentation technique, which provides extensive backbone fragmentation that can be complementary in sequence coverage to the aforementioned electron-based fragmentation techniques. Here, we explore the application of electrospray ionization (ESI)-UVPD FTMS on an Orbitrap Fusion Lumos Tribrid mass spectrometer to top-down HDX analysis of proteins. We have incorporated UVPD-specific fragment-ion types and fragment-ion mixtures into our isotopic envelope fitting software (HDX Match) for the top-down HDX analysis. We have shown that UVPD data is complementary to ETD, thus improving the overall resolution when used as a combined approach.

Surface State Dynamics of Topological Insulators Investigated by Femtosecond Time- and Angle-Resolved Photoemission Spectroscopy

Directory of Open Access Journals (Sweden)

Hamoon Hedayat

2018-04-01

Full Text Available Topological insulators (TI are known for striking quantum phenomena associated with their spin-polarized topological surface state (TSS. The latter in particular forms a Dirac cone that bridges the energy gap between valence and conduction bands, providing a unique opportunity for prospective device applications. In TI of the BixSb2−xTeySe3−y (BSTS family, stoichiometry determines the morphology and position of the Dirac cone with respect to the Fermi level. In order to engineer specific transport properties, a careful tuning of the TSS is highly desired. Therefore, we have systematically explored BSTS samples with different stoichiometries by time- and angle-resolved photoemission spectroscopy (TARPES. This technique provides snapshots of the electronic structure and discloses the carrier dynamics in surface and bulk states, providing crucial information for the design of electro-spin current devices. Our results reveal the central role of doping level on the Dirac cone structure and its femtosecond dynamics. In particular, an extraordinarily long TSS lifetime is observed when the the vertex of the Dirac cone lies at the Fermi level.

Far-infrared and submillimeter spectroscopy of photodissociation regions

International Nuclear Information System (INIS)

Qaiyum, A.

1993-12-01

The physical properties of the galactic and extragalactic photodissociation regions, warm gas components molecular clouds are, generally, derived through the far-infrared (FIR) fine structure and submillimeter line emissions arising out of these regions. In the theoretical studies of these lines the model of Tielens and Hollenbach (herein after referred as TH) are usually employed in which all the opacity is assumed local in escape probability formalism and inward directed photons do not escape. These assumptions are contrary to the observational facts, where most of the lines are found optically thin except OI (63 μm) and low rotational transitions of CO and some other molecules. The optically thin medium will allow the radiation to escape through any face of the region. These observational evidences let us to assume finite parallel plane slab, instead of semi-infinite parallel slab, in which the photons are allowed to escape from both surfaces (back and front). In the present study an attempt has been made to incorporate the two sided escape of photons from the PDRs and to study its effect on the FIR and submillimeter line emission from the PDRs/molecular clouds. Further the present formalism is also employed to study the clumpy PDRs/molecular clouds. The preliminary results show that now serious consequences are found on the thermal and chemical structure of the regions but individual line emissions are modified by differing factors. Particularly at low density and low kinetic temperature the change is substantial but at density greater than the critical density of the line and temperature close to the excitation temperature its effect is almost negligible. An attempt has also been made to study the physical conditions of the M17 region employing the present formalism. (author). 49 refs, 8 figs, 1 tab

Dynamic Time-Resolved Chirped-Pulse Rotational Spectroscopy of Vinyl Cyanide Photoproducts in a Room Temperature Flow Reactor

Science.gov (United States)

Zaleski, Daniel P.; Prozument, Kirill

2017-06-01

Chirped-pulsed (CP) Fourier transform rotational spectroscopy invented by Brooks Pate and coworkers a decade ago is an attractive tool for gas phase chemical dynamics and kinetics studies. A good reactor for such a purpose would have well-defined (and variable) temperature and pressure conditions to be amenable to accurate kinetic modeling. Furthermore, in low pressure samples with large enough number of molecular emitters, reaction dynamics can be observable directly, rather than mediated by supersonic expansion. In the present work, we are evaluating feasibility of in situ time-resolved CP spectroscopy in a room temperature flow tube reactor. Vinyl cyanide (CH_2CHCN), neat or mixed with inert gasses, flows through the reactor at pressures 1-50 μbar (0.76-38 mTorr) where it is photodissociated by a 193 nm laser. Millimeter-wave beam of the CP spectrometer co-propagates with the laser beam along the reactor tube and interacts with nascent photoproducts. Rotational transitions of HCN, HNC, and HCCCN are detected, with ≥10 μs time-steps for 500 ms following photolysis of CH_2CHCN. The post-photolysis evolution of the photoproducts' rotational line intensities is investigated for the effects of rotational and vibrational thermalization of energized photoproducts. Possible contributions from bimolecular and wall-mediated chemistry are evaluated as well.

Femtosecond time-resolved transient absorption spectroscopy of xanthophylls.

Science.gov (United States)

Niedzwiedzki, Dariusz M; Sullivan, James O; Polívka, Tomás; Birge, Robert R; Frank, Harry A

2006-11-16

Xanthophylls are a major class of photosynthetic pigments that participate in an adaptation mechanism by which higher plants protect themselves from high light stress. In the present work, an ultrafast time-resolved spectroscopic investigation of all the major xanthophyll pigments from spinach has been performed. The molecules are zeaxanthin, lutein, violaxanthin, and neoxanthin. beta-Carotene was also studied. The experimental data reveal the inherent spectral properties and ultrafast dynamics including the S(1) state lifetimes of each of the pigments. In conjunction with quantum mechanical computations the results address the molecular features of xanthophylls that control the formation and decay of the S* state in solution. The findings provide compelling evidence that S* is an excited state with a conformational geometry twisted relative to the ground state. The data indicate that S* is formed via a branched pathway from higher excited singlet states and that its yield depends critically on the presence of beta-ionylidene rings in the polyene system of pi-electron conjugated double bonds. The data are expected to be beneficial to researchers employing ultrafast time-resolved spectroscopic methods to investigate the mechanisms of both energy transfer and nonphotochemical quenching in higher plant preparations.

Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

Science.gov (United States)

Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

2018-01-16

Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

Science.gov (United States)

Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

2018-01-01

Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

Energy Technology Data Exchange (ETDEWEB)

Wu, Guorong [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Neville, Simon P. [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Schalk, Oliver [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, AlbaNova University Center, Stockholm University, Roslagstullsbacken 21, 106 91 Stockholm (Sweden); Sekikawa, Taro [Department of Applied Physics, Hokkaido University, Kita-13 Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Ashfold, Michael N. R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Worth, Graham A. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Stolow, Albert, E-mail: astolow@uottawa.ca [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario K1N 6N5 (Canada)

2016-01-07

The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A{sub 2}(πσ{sup ∗}) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B{sub 1}(π3p{sub y}) Rydberg state, followed by prompt internal conversion to the A{sub 2}(πσ{sup ∗}) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A{sub 2}(πσ{sup ∗}) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A{sub 2}(πσ{sup ∗}) state, facilitating wavepacket motion around the potential barrier in the N–CH{sub 3} dissociation coordinate.

Excited state non-adiabatic dynamics of N-methylpyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

International Nuclear Information System (INIS)

Wu, Guorong; Neville, Simon P.; Schalk, Oliver; Sekikawa, Taro; Ashfold, Michael N. R.; Worth, Graham A.; Stolow, Albert

2016-01-01

The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A 2 (πσ ∗ ) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B 1 (π3p y ) Rydberg state, followed by prompt internal conversion to the A 2 (πσ ∗ ) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A 2 (πσ ∗ ) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A 2 (πσ ∗ ) state, facilitating wavepacket motion around the potential barrier in the N–CH 3 dissociation coordinate

Angle-resolved photoemission investigation of SmB{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Hlawenka, Peter; Rader, Oliver; Siemensmeyer, Konrad; Weschke, Eugen; Varykhalov, Andrei; Rienks, Emile [Helmholtz-Zentrum Berlin (Germany); Shitsevalova, Natalya [Institute for Problems of Material Science, Kiev (Ukraine); Gabani, Slavomir; Flachbart, Karol [IEP, Slovak Academy of Science, Kosice (Slovakia)

2015-07-01

Recently the mixed valence compound SmB{sub 6} has drawn great attention. Theoretically predicted surface states, which should result from a hybridisation of localised f-bands with conduction electrons and a band inversion, would make SmB{sub 6} the first realisation of a so called topological Kondo insulator. Conductivity and transport measurements, as well as spin-resolved photoemission spectroscopy seem to fortify the scenario of a topological nature of the conductive surface. We investigate the surface electronic structure of SmB{sub 6} by means of high resolution angle-resolved photoemission spectroscopy measurements below 1 K. We will present new insights into the surface states that determine the low temperature conductivity of this material.

Angle-resolved photoemission extended fine structure: Multiple layers of emitters and multiple initial states

International Nuclear Information System (INIS)

Huff, W.R.A.; Kellar, S.A.; Moler, E.J.; California Univ., Berkeley, CA; Chen, Y.; Wu, H.; Shirley, D.A.; Hussain, Z.

1995-01-01

Recently, angle-resolved photoemission extended fine structure (ARPEFS) has been applied to experimental systems involving multiple layers of emitters and non-s core-level photoemission in an effort to broaden the utility of the technique. Most of the previous systems have been comprised of atomic or molecular overlayers adsorbed onto a single-crystal, metal surface and the photoemission data were taken from an s atomic core-level in the overlayer. For such a system, the acquired ARPEFS data is dominated by the p o final state wave backscattering from the substrate atoms and is well understood. In this study, we investigate ARPEFS as a surface-region structure determination technique when applied to experimental systems comprised of multiple layers of photoemitters and arbitrary initial state core-level photoemission. Understanding the data acquired from multiple layers of photoemitters is useful for studying multilayer interfaces, ''buried'' surfaces, and clean crystals in ultra- high vacuum. The ability to apply ARPEFS to arbitrary initial state core-level photoemission obviously opens up many systems to analysis. Efforts have been ongoing to understand such data in depth. We present clean Cu(111) 3s, 3p, and 3d core-level, normal photoemission data taken on a high resolution soft x-ray beamline 9.3.2 at the Advanced Light Source in Berkeley, California and clean Ni(111) 3p normal photoemission data taken at the National Synchrotron Light Source in Upton, New York, USA

Photoabsorption and photodissociation studies of dimethyl sulphoxide (DMSO) in the 35,000-80,000 cm-1 region using synchrotron radiation

Science.gov (United States)

Mandal, Anuvab; Singh, Param Jeet; Shastri, Aparna; Sunanda, K.; Jagatap, B. N.

2015-05-01

Photoabsorption and photodissociation studies of dimethyl sulphoxide and its deuterated isotopologue (DMSO-h6 and DMSO-d6) are performed using synchrotron radiation in the 35,000-80,000 cm-1 region. In the photoabsorption spectrum, Rydberg series converging to the first three ionization potentials of DMSO at 9.1, 10.1 and 12.3 eV corresponding to removal of an electron from the highest three occupied molecular orbitals (14a‧, 7a″ and 13a‧) are observed. Based on a quantum defect analysis, Rydberg series assignments are extended to higher members as compared to earlier works and a few ambiguities in earlier assignments are clarified. Analysis is aided by quantum chemical calculations using the DFT and TDDFT methodologies. Vibronic structures observed in the spectrum of DMSO-h6 in the regions 7.7-8.1 eV and 8.1-8.8 eV are attributed to the transitions 7a″→4p at 7.862 eV and 14a‧→6s/4d at 8.182 eV, respectively. Photoabsorption spectra of DMSO-h6 and -d6 recorded using a broad band incident radiation show prominent peaks, which are identified and assigned to electronic and vibronic transitions of the SO radical. This provides a direct confirmation of the fact that DMSO preferentially dissociates into CH3 and SO upon UV-VUV excitation, as proposed in earlier photodissociation studies. An extended vibronic band system associated with the e1Π-X3Σ- transition of the SO radical is identified and assigned. The complete VUV photoabsorption spectrum of DMSO-d6 is also reported here for the first time.

Infrared photodissociation spectroscopy of M(N2)n(+) (M = Y, La, Ce; n = 7-8) in the gas phase.

Science.gov (United States)

Xie, Hua; Shi, Lei; Xing, Xiaopeng; Tang, Zichao

2016-02-14

M(N2)n(+) (M = Y, La, Ce; n = 7-8) complexes have been studied by infrared photodissociation (IRPD) spectroscopy and density functional theory (DFT) calculations. The experimental results indicate that the N-N stretching vibrational frequencies are red-shifted from the gas-phase N2 value. The π back-donation is found to be a main contributor in these systems. IRPD spectra and DFT calculations reveal the coexistence of two isomers in the seven-coordinate M(N2)7(+) and eight-coordinate M(N2)8(+) complexes, respectively. The present studies on these metal-nitrogen complexes shed light on the interactions and coordinations toward N2 with transition and lanthanide metals.

Characterization of hydrogen bonding motifs in proteins: hydrogen elimination monitoring by ultraviolet photodissociation mass spectrometry.

Science.gov (United States)

Morrison, Lindsay J; Chai, Wenrui; Rosenberg, Jake A; Henkelman, Graeme; Brodbelt, Jennifer S

2017-08-02

Determination of structure and folding of certain classes of proteins remains intractable by conventional structural characterization strategies and has spurred the development of alternative methodologies. Mass spectrometry-based approaches have a unique capacity to differentiate protein heterogeneity due to the ability to discriminate populations, whether minor or major, featuring modifications or complexation with non-covalent ligands on the basis of m/z. Cleavage of the peptide backbone can be further utilized to obtain residue-specific structural information. Here, hydrogen elimination monitoring (HEM) upon ultraviolet photodissociation (UVPD) of proteins transferred to the gas phase via nativespray ionization is introduced as an innovative approach to deduce backbone hydrogen bonding patterns. Using well-characterized peptides and a series of proteins, prediction of the engagement of the amide carbonyl oxygen of the protein backbone in hydrogen bonding using UVPD-HEM is demonstrated to show significant agreement with the hydrogen-bonding motifs derived from molecular dynamics simulations and X-ray crystal structures.

Improved production of Br atoms near zero speed by photodissociating laser aligned Br2 molecules.

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Deng, L Z; Yin, J P

2014-10-28

We theoretically investigated the improvement on the production rate of the decelerated bromine (Br) atoms near zero speed by photodissociating laser aligned Br2 precursors. Adiabatic alignment of Br2 precursors exposed to long laser pulses with duration on the order of nanoseconds was investigated by solving the time-dependent Schrödinger equation. The dynamical fragmentation of adiabatically aligned Br2 precursors was simulated and velocity distribution of the Br atoms produced was analyzed. Our study shows that the larger the degree of the precursor alignment, ⟨cos(2) θ⟩, the higher the production rate of the decelerated Br atoms near zero speed. For Br2 molecules with an initial rotational temperature of ~1 K, a ⟨cos(2) θ⟩ value of ~0.88 can result in an improvement factor of over ~20 on the production rate of the decelerated Br atoms near zero speed, requiring a laser intensity of only ~1 × 10(12) W/cm(2) for alignment.

Time-resolved resonance Raman spectroscopy of radiation-chemical processes

International Nuclear Information System (INIS)

Tripathi, G.N.R.

1983-01-01

A tunable pulsed laser Raman spectrometer for time resolved Raman studies of radiation-chemical processes is described. This apparatus utilizes the state of art optical multichannel detection and analysis techniques for data acquisition and electron pulse radiolysis for initiating the reactions. By using this technique the resonance Raman spectra of intermediates with absorption spectra in the 248-900 nm region, and mean lifetimes > 30 ns can be examined. This apparatus can be used to time resolve the vibrational spectral overlap between transients absorbing in the same region, and to follow their decay kinetics by monitoring the well resolved Raman peaks. For kinetic measurements at millisecond time scale, the Raman technique is preferable over optical absorption method where low frequency noise is quite bothersome. A time resolved Raman study of the pulse radiolytic oxidation of aqueous tetrafluorohydroquinone and p-methoxyphenol is briefly discussed. 15 references, 5 figures

Theoretical study of the mechanism of formation of a chemical bond between two ions: A+ and B+. Application to CO++. Interpretation of N2O++ photo-dissociation mechanisms

International Nuclear Information System (INIS)

Levasseur, Nathalie

1989-01-01

This research thesis reports the theoretical study of the mechanism of formation of a chemical bond between two positively charged species, within the frame of the valence-bond theory and in the CO model case. The analysis in terms of orthogonal and non orthogonal orbitals leads to two very different interpretations, and allows potential curves of doubly charged diatomic ions to be simply explained, the generally evoked model to be put into question again, and a predictive model to be developed. The theoretical determination of N 2 O potential energy surfaces and of the first states of N 2 O ++ ( 3 Σ - , 1 Δ, 1 Σ + et 3 Π) allowed experimental results of N 2 O ++ photo-dissociation to be at least qualitatively understood and interpreted. Moreover, the study of electronic configurations involved in dissociation, showed that the model elaborated for a diatomic molecule is also valid for a triatomic system [fr

Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces

Science.gov (United States)

Zutz, Amelia Marie

Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.

Rotationally resolved state-to-state photoionization and the photoelectron study of vanadium monocarbide and its cations (VC/VC(+)).

Science.gov (United States)

Chang, Yih Chung; Luo, Zhihong; Pan, Yi; Zhang, Zheng; Song, Ying-Nan; Kuang, Sophie Yajin; Yin, Qing Zhu; Lau, Kai-Chung; Ng, C Y

2015-04-21

By employing two-color visible (VIS)-ultraviolet (UV) laser photoionization and pulsed field ionization-photoelectron (PFI-PE) techniques, we have obtained highly rotationally resolved photoelectron spectra for vanadium monocarbide cations (VC(+)). The state-to-state VIS-UV-PFI-PE spectra thus obtained allow unambiguous assignments for the photoionization rotational transitions, resulting in a highly precise value for the adiabatic ionization energy (IE) of vanadium monocarbide (VC), IE(VC) = 57512.0 ± 0.8 cm(-1) (7.13058 ± 0.00010 eV), which is defined as the energy of the VC(+)(X(3)Δ1; v(+) = 0; J(+) = 1) ← VC(X(2)Δ3/2; v'' = 0; J'' = 3/2) photoionization transition. The spectroscopic constants for VC(+)(X(3)Δ1) determined in the present study include the harmonic vibrational frequency ωe(+) = 896.4 ± 0.8 cm(-1), the anharmonicity constant ωe(+)xe(+) = 5.7 ± 0.8 cm(-1), the rotational constants Be(+) = 0.6338 ± 0.0025 cm(-1) and αe(+) = 0.0033 ± 0.0007 cm(-1), the equilibrium bond length re(+) = 1.6549 ± 0.0003 Å, and the spin-orbit coupling constant A = 75.2 ± 0.8 cm(-1) for VC(+)(X(3)Δ1,2,3). These highly precise energetic and spectroscopic data are used to benchmark state-of-the-art CCSDTQ/CBS calculations. In general, good agreement is found between the theoretical predictions and experimental results. The theoretical calculations yield the values, IE(VC) = 7.126 eV; the 0 K bond dissociation energies: D0(V-C) = 4.023 eV and D0(V(+)-C) = 3.663 eV; and heats of formation: ΔH°(f0)(VC) = 835.2, ΔH°(f298)(VC) = 840.4, ΔH°(f0)(VC(+)) = 1522.8, and ΔH°(f298)(VC(+)) = 1528.0 kJ mol(-1).

Isotope separation of 17O by photodissociation of ozone with near-infrared laser irradiation

Science.gov (United States)

Hayashida, Shigeru; Kambe, Takashi; Sato, Tetsuya; Igarashi, Takehiro; Kuze, Hiroaki

2012-04-01

Oxygen-17 is a stable oxygen isotope useful for various diagnostics in both engineering and medical applications. Enrichment of 17O, however, has been very costly due to the lack of appropriate methods that enable efficient production of 17O on an industrial level. In this paper, we report the first 17O-selective photodissociation of ozone at a relatively high pressure, which has been achieved by irradiating a gas mixture of 10 vol% O3-90 vol% CF4 with narrowband laser. The experiment was conducted on a pilot-plant scale. A total laser power of 1.6 W was generated by external-cavity diode lasers with all the laser wavelengths fixed at the peak of an absorption line of 16O16O17O around 1 μm. The beams were introduced into a 25 -m long photoreaction cell under the sealed-off condition with a total pressure of 20 kPa. Lower cell temperature reduced the background decomposition of ozone, and at the temperature of 158 K, an 17O enrichment factor of 2.2 was attained.

Time-resolved x-ray absorption spectroscopy: Watching atoms dance

Science.gov (United States)

Milne, Chris J.; Pham, Van-Thai; Gawelda, Wojciech; van der Veen, Renske M.; El Nahhas, Amal; Johnson, Steven L.; Beaud, Paul; Ingold, Gerhard; Lima, Frederico; Vithanage, Dimali A.; Benfatto, Maurizio; Grolimund, Daniel; Borca, Camelia; Kaiser, Maik; Hauser, Andreas; Abela, Rafael; Bressler, Christian; Chergui, Majed

2009-11-01

The introduction of pump-probe techniques to the field of x-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [FeII(bpy)3]2+, in aqueous solution, resolving the Fe-N bond distance elongation as 0.2 Å. In addition an analysis technique using the reduced χ2 goodness of fit between FEFF EXAFS simulations and the experimental transient absorption signal in energy space has been successfully tested as a function of excited state population and chemical shift, demonstrating its applicability in situations where the fractional excited state population cannot be determined through other measurements. Finally by using a novel ultrafast hard x-ray 'slicing' source the question of how the molecule relaxes after optical excitation has been successfully resolved using femtosecond XANES.

Asymmetric valley-resolved beam splitting and incident modes in slanted graphene junctions

International Nuclear Information System (INIS)

Hsieh, S. H.; Chu, C. S.

2016-01-01

Electron injection into a graphene sheet through a slanted armchair graphene nanoribbon (AGNR) is investigated. An incident mode, or subband, in the AGNR is valley-unpolarized. Our attention is on the valley-resolved nature of the injected electron beams and its connection to the incident mode. It is known for a normal injection that an incident mode will split symmetrically into two valley-resolved beams of equal intensity. We show, in contrast, that slanted injections result in asymmetric valley-resolved beam splitting. The most asymmetric beam splitting cases, when one of the valley-resolved beams has basically disappeared, are found and the condition derived. This is shown not due to trigonal warping because it holds even in the low incident energy regime, as long as collimation allows. These most asymmetric beam splitting cases occur at energies within an energy interval near and include the subband edge of an incident mode. The physical picture is best illustrated by a projection of the slanted AGNR subband states onto that of the 2D graphene sheet. It follows that the disappearing of a valley-resolved beam coincides with the situation that the group velocities of the projected states in the corresponding valley are in backward directions

Time-resolved spectroscopy defines perturbation in molecules

International Nuclear Information System (INIS)

Ahmed, K.

1998-01-01

Time-resolved LIF spectroscopy is employed in order to investigate perturbations in different excited electronic state of alkali molecules. Dunham Coefficients are used to search the selected excited ro-vibrational level, which is overlap with the other nearby excited states. Lifetime measurement has been performed of more than 50 ro-vibrational levels. Out of these 25 levels were observed drastically different lifetimes from the other unperturbed levels. In this report, influence of different perturbations on this anomalous behavior is investigated and discussed. (author)

Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization.

Science.gov (United States)

Amini, Kasra; Savelyev, Evgeny; Brauße, Felix; Berrah, Nora; Bomme, Cédric; Brouard, Mark; Burt, Michael; Christensen, Lauge; Düsterer, Stefan; Erk, Benjamin; Höppner, Hauke; Kierspel, Thomas; Krecinic, Faruk; Lauer, Alexandra; Lee, Jason W L; Müller, Maria; Müller, Erland; Mullins, Terence; Redlin, Harald; Schirmel, Nora; Thøgersen, Jan; Techert, Simone; Toleikis, Sven; Treusch, Rolf; Trippel, Sebastian; Ulmer, Anatoli; Vallance, Claire; Wiese, Joss; Johnsson, Per; Küpper, Jochen; Rudenko, Artem; Rouzée, Arnaud; Stapelfeldt, Henrik; Rolles, Daniel; Boll, Rebecca

2018-01-01

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon-iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

Kinetics of photodissociated oxygen recombination to human oxyhemoglobin

International Nuclear Information System (INIS)

Bokut', S.B.; Syakhovich, V.E.; Parul', D.A.; Lepeshkevich, S.V.; Dzhagarov, B.M.

2001-01-01

Oxygen binding to the tetrameric hemoglobin (Hb) is a basic reaction for study of a cooperativity and allosteric homotropic and heterotropic interactions in proteins. In tetrameric hemoglobin the certain sites in the α 1 β 2 -interface have the precise geometry and chemical reactivity to bind 2,3-diphosphoglycerate, protons, chloride and hence shift the equilibrium away from the oxyconformation, thereby favoring O 2 release. Post-translational modifications of the major hemoglobin fraction Hb A 1 with sugar moiety in the Hb central cavity leads to differences in geometry of the effectors binding region providing a useful experimental tool to study the long range relationship in the tetramer molecule. Here we present the results of the nongeminate biomolecular association of Hb and O 2 obtained by nanosecond laser flash-photolysis. All measurements were carried out in 50 mM potassium-phosphate buffer pH 7.4 with the following samples Hb A 1 , HbA 1c , HbA 1b , and HbA 1 in the presence of the tenfold excess of inositol hexaphosphate (IHP). Our results show that oxygen recombination kinetics are characterized by two processes with different decay times and Hb-form-dependent contributions. This process can be described by the following expression: A(t)=A 1 exp(-t/τ 1 )+A 2 exp(-t/τ 2 ), where A(t) is a normalized number of the deoxy-Hb molecules. The short-live component has a lifetime τ 1 , which is Hb-type dependent and changes in the intervals 30-60 μs, the second component has a lifetime τ 2 around 100 μs, and also is sample-dependent value. A(t=0) is proportional to apparent quantum yields of the photodissociation and determines by geminate stages of oxygen binding to Fe from the protein matrix areas. These results show that post-translational modifications of the major hemoglobin component HbA 1 have influence on hemoglobin transport function via the long range relationship in the tetramer molecule

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Indian Academy of Sciences (India)

R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

towards the z = 1.2 Red Quasar 3C 190, 37. Navabi Ali Akbar Is the Age Problem Resolved?, 3. Pandey Sanjay, K. see Bharadwaj Somnath, 23. Papadopoulos, N. J. see Caranicolas, N. D., 85. Qaiyum Abdul Studies of Clump Structure of Photodissociation Regions at Mil- limeter and Sub-millimeter Wavelengths, 69.

Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

Science.gov (United States)

Wang, Y F; Singh, Shashi B; Limaye, Mukta V; Shao, Y C; Hsieh, S H; Chen, L Y; Hsueh, H C; Wang, H T; Chiou, J W; Yeh, Y C; Chen, C W; Chen, C H; Ray, Sekhar C; Wang, J; Pong, W F; Takagi, Y; Ohigashi, T; Yokoyama, T; Kosugi, N

2015-10-20

This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

International Nuclear Information System (INIS)

Billard, I.; Luetzenkirchen, K.

2003-01-01

Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

Dissociation of metastable CH3CO radicals studied by time-resolved photofragment imaging

Science.gov (United States)

Suzuki, Toshinori; Shibata, Takeshi; Li, Haiyang

1998-05-01

A novel experimental technique to measure the energy- dependent unimolecular dissociation rate k(E) of radical species is presented. Internally excited CH3CO radicals were formed by ultraviolet photodissociation of CH3COCl, and the subsequent decay of these radicals was detected by subpicosecond time-clocked photofragment imaging. The CH3CO radicals with different internal energies were dispersed in space by their recoil velocities, and their decay rates were measured for each internal energy.

Resolving deconvolution ambiguity in gene alternative splicing

Directory of Open Access Journals (Sweden)

Hubbell Earl

2009-08-01

Full Text Available Abstract Background For many gene structures it is impossible to resolve intensity data uniquely to establish abundances of splice variants. This was empirically noted by Wang et al. in which it was called a "degeneracy problem". The ambiguity results from an ill-posed problem where additional information is needed in order to obtain an unique answer in splice variant deconvolution. Results In this paper, we analyze the situations under which the problem occurs and perform a rigorous mathematical study which gives necessary and sufficient conditions on how many and what type of constraints are needed to resolve all ambiguity. This analysis is generally applicable to matrix models of splice variants. We explore the proposal that probe sequence information may provide sufficient additional constraints to resolve real-world instances. However, probe behavior cannot be predicted with sufficient accuracy by any existing probe sequence model, and so we present a Bayesian framework for estimating variant abundances by incorporating the prediction uncertainty from the micro-model of probe responsiveness into the macro-model of probe intensities. Conclusion The matrix analysis of constraints provides a tool for detecting real-world instances in which additional constraints may be necessary to resolve splice variants. While purely mathematical constraints can be stated without error, real-world constraints may themselves be poorly resolved. Our Bayesian framework provides a generic solution to the problem of uniquely estimating transcript abundances given additional constraints that themselves may be uncertain, such as regression fit to probe sequence models. We demonstrate the efficacy of it by extensive simulations as well as various biological data.

Mechanisms of Diurnal Precipitation over the United States Great Plains: A Cloud-Resolving Model Simulation

Science.gov (United States)

Lee, M.-I.; Choi, I.; Tao, W.-K.; Schubert, S. D.; Kang, I.-K.

2010-01-01

The mechanisms of summertime diurnal precipitation in the US Great Plains were examined with the two-dimensional (2D) Goddard Cumulus Ensemble (GCE) cloud-resolving model (CRM). The model was constrained by the observed large-scale background state and surface flux derived from the Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Program s Intensive Observing Period (IOP) data at the Southern Great Plains (SGP). The model, when continuously-forced by realistic surface flux and large-scale advection, simulates reasonably well the temporal evolution of the observed rainfall episodes, particularly for the strongly forced precipitation events. However, the model exhibits a deficiency for the weakly forced events driven by diurnal convection. Additional tests were run with the GCE model in order to discriminate between the mechanisms that determine daytime and nighttime convection. In these tests, the model was constrained with the same repeating diurnal variation in the large-scale advection and/or surface flux. The results indicate that it is primarily the surface heat and moisture flux that is responsible for the development of deep convection in the afternoon, whereas the large-scale upward motion and associated moisture advection play an important role in preconditioning nocturnal convection. In the nighttime, high clouds are continuously built up through their interaction and feedback with long-wave radiation, eventually initiating deep convection from the boundary layer. Without these upper-level destabilization processes, the model tends to produce only daytime convection in response to boundary layer heating. This study suggests that the correct simulation of the diurnal variation in precipitation requires that the free-atmospheric destabilization mechanisms resolved in the CRM simulation must be adequately parameterized in current general circulation models (GCMs) many of which are overly sensitive to the parameterized boundary layer heating.

Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm

Science.gov (United States)

Sullivan, Erin N.; Nichols, Bethan; Neumark, Daniel M.

2018-01-01

The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH3OO) and ethyl peroxy (C2H5OO), are investigated using fast beam photofragment translational spectroscopy. A fast beam of CH3OO- or C2H5OO- anions is photodetached to generate neutral radicals that are subsequently dissociated using 248 nm photons. The coincident detection of the photofragment positions and arrival times allows for the determination of mass, translational energy, and angular distributions for both two-body and three-body dissociation events. CH3OO exhibits repulsive O loss resulting in the formation of O(1D) + CH3O with high translational energy release. Minor two-body channels leading to OH + CH2O and CH3O + O(3P) formation are also detected. In addition, small amounts of H + O(3P) + CH2O are observed and attributed to O loss followed by CH3O dissociation. C2H5OO exhibits more complex dissociation dynamics, in which O loss and OH loss occur in roughly equivalent amounts with O(1D) formed as the dominant O atom electronic state via dissociation on a repulsive surface. Minor two-body channels leading to the formation of O2 + C2H5 and HO2 + C2H4 are also observed and attributed to a ground state dissociation pathway following internal conversion. Additionally, C2H5OO dissociation yields a three-body product channel, CH3 + O(3P) + CH2O, for which the proposed mechanism is repulsive O loss followed by the dissociation of C2H5O over a barrier. These results are compared to a recent study of tert-butyl peroxy (t-BuOO) in which 248 nm excitation results in three-body dissociation and ground state two-body dissociation but no O(1D) production.

Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm

International Nuclear Information System (INIS)

Blank, D.A.; North, S.W.; Stranges, D.

1997-01-01

When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH 3 SOCH 3 ) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH 3 intermediate prior to dissociation to define a stepwise dissociation: (1) CH 3 SOCH 3 → 2CH 3 + SO; (2a) CH 3 SOCH 3 → CH 3 + SOCH 3 ; and (2b) SOCH 3 → SO + CH 3 . Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH 3 and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 9.0.2.1. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH 3 intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2

Photoelectron and photodissociation studies of free atoms and molecules, using synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Medhurst, L.J.

1991-11-01

High resolution synchrotron radiation and Zero-Kinetic-Energy Photoelectron spectroscopy were used to study two-electron transitions in atomic systems at their ionization thresholds. Using this same technique the core-ionized mainline and satellite states of N{sub 2} and CO were studied with vibrational resolution. Vibrationally resolved synchrotron radiation was used to study the dissociation of N{sub 2}, C{sub 2}H{sub 4}, and CH{sub 3}Cl near the N 1s and C 1s thresholds. The photoelectron satellites of the argon 3s, krypton 4s and xenon 4d subshells were studied with zero kinetic energy photoelectron spectroscopy at their ionization thresholds. In all of these cases, satellites with lower binding energies are enhanced at their thresholds while those closer to the double ionization threshold are suppressed relative to their intensities at high incident light energies.

Photoelectron and photodissociation studies of free atoms and molecules, using synchrotron radiation

International Nuclear Information System (INIS)

Medhurst, L.J.

1991-11-01

High resolution synchrotron radiation and Zero-Kinetic-Energy Photoelectron spectroscopy were used to study two-electron transitions in atomic systems at their ionization thresholds. Using this same technique the core-ionized mainline and satellite states of N 2 and CO were studied with vibrational resolution. Vibrationally resolved synchrotron radiation was used to study the dissociation of N 2 , C 2 H 4 , and CH 3 Cl near the N 1s and C 1s thresholds. The photoelectron satellites of the argon 3s, krypton 4s and xenon 4d subshells were studied with zero kinetic energy photoelectron spectroscopy at their ionization thresholds. In all of these cases, satellites with lower binding energies are enhanced at their thresholds while those closer to the double ionization threshold are suppressed relative to their intensities at high incident light energies

Investigations towards multi-step laser spectroscopy of stored H{sub 3}{sup +} molecular ions; Untersuchungen zur Mehrstufen-Laserspektroskopie an gespeicherten H{sub 3}{sup +}-Molekuelionen

Energy Technology Data Exchange (ETDEWEB)

Bing, Dennis

2010-07-21

The triatomic H{sub 3}{sup +} molecular ion plays an important role in molecular quantum dynamics through its equilateral triangular structure. Many studies of molecular reactions involving H{sub 3}{sup +} have been done thus far, among them dissociative recombination in storage ring experiments with a cold electron-beam. For these strongly energy dependent reactions, the population in individual rovibrational levels is of large importance. To determine such populations for H{sub 3}{sup +} ions inside a storage ring, an extremely sensitive state-selective method must be used, such as the Resonant- Enhanced Multi-Photon Dissociation (REMPD). In REMPD, molecules are highly excited from a low lying initial level in a first resonant step and photodissociated from these high lying states in a second step. To fully employ this method, detailed investigations are necessary. Here, an experiment is presented which determines the energy range of the highly excited vibrational states of H{sub 3}{sup +} suitable for photodissociation. Additional photodissociation experiments, using hot H{sub 3}{sup +} ions in the storage ring TSR at the Max-Planck Institute for Nuclear Physics, yield an effective lifetime of these dissociated H{sub 3}{sup +} states. Finally selective vibrational excitation of cold H{sub 3}{sup +} (the rst step of REMPD) is discussed with the aim of reaching the highly excited vibrational states suitable for photodissociation. (orig.)

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...

Numerical simulations of time-resolved quantum electronics

International Nuclear Information System (INIS)

Gaury, Benoit; Weston, Joseph; Santin, Matthieu; Houzet, Manuel; Groth, Christoph; Waintal, Xavier

2014-01-01

Numerical simulation has become a major tool in quantum electronics both for fundamental and applied purposes. While for a long time those simulations focused on stationary properties (e.g. DC currents), the recent experimental trend toward GHz frequencies and beyond has triggered a new interest for handling time-dependent perturbations. As the experimental frequencies get higher, it becomes possible to conceive experiments which are both time-resolved and fast enough to probe the internal quantum dynamics of the system. This paper discusses the technical aspects–mathematical and numerical–associated with the numerical simulations of such a setup in the time domain (i.e. beyond the single-frequency AC limit). After a short review of the state of the art, we develop a theoretical framework for the calculation of time-resolved observables in a general multiterminal system subject to an arbitrary time-dependent perturbation (oscillating electrostatic gates, voltage pulses, time-varying magnetic fields, etc.) The approach is mathematically equivalent to (i) the time-dependent scattering formalism, (ii) the time-resolved non-equilibrium Green’s function (NEGF) formalism and (iii) the partition-free approach. The central object of our theory is a wave function that obeys a simple Schrödinger equation with an additional source term that accounts for the electrons injected from the electrodes. The time-resolved observables (current, density, etc.) and the (inelastic) scattering matrix are simply expressed in terms of this wave function. We use our approach to develop a numerical technique for simulating time-resolved quantum transport. We find that the use of this wave function is advantageous for numerical simulations resulting in a speed up of many orders of magnitude with respect to the direct integration of NEGF equations. Our technique allows one to simulate realistic situations beyond simple models, a subject that was until now beyond the simulation

The role of mediation in resolving workplace relationship conflict.

Science.gov (United States)

McKenzie, Donna Margaret

2015-01-01

Stress triggered by workplace-based interpersonal conflict can result in damaged relationships, loss of productivity, diminished job satisfaction and increasingly, workers' compensation claims for psychological injury. This paper examined the literature on the role and effectiveness of mediation, as the most common method of Alternative Dispute Resolution, in resolving workplace relationship conflict. Available evidence suggests that mediation is most effective when supported by organisational commitment to ADR strategies, policies and processes, and conducted by independent, experienced and qualified mediators. The United States Postal Service program REDRESS™ is described as an illustration of the successful use of mediation to resolve conflict in the workplace. Copyright © 2015 Elsevier Ltd. All rights reserved.

Photodissociation of C3H5Br and C4H7Br at 234 nm

International Nuclear Information System (INIS)

Kim, Hyun Kook; Paul, Dababrata; Hong, Ki Ryong; Cho, Ha Na; Kim, Tae Kyu; Lee, Kyoung Seok

2012-01-01

The photodissociation dynamics of cyclopropyl bromide (C-3H 5 Br) and cyclobutyl bromide (C 4 H 7 Br) at 234 nm was investigated. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br( 2 P 3/2 ) and Br*( 2 P 1/2 ) atoms. The recoil anisotropies for the Br and Br* channels were measured to be βBr = 0.92 ± 0.03 and βBr* = 1.52 ± 0.04 for C 3 H 5 Br and βBr = 1.10 ± 0.03 and βBr* = 1.49 ± 0.05 for C 4 H 7 Br. The relative quantum yield for Br was found to be ΦBr = 0.13 ± 0.03 and for C 3 H 5 Br and C 4 H 7 Br, respectively. The soft radical limit of the impulsive model adequately modeled the related energy partitioning. The nonadiabatic transition probability from the 3A' and 4A' potential energy surfaces was estimated and discussed

Radical Rearrangement Chemistry in Ultraviolet Photodissociation of Iodotyrosine Systems: Insights from Metastable Dissociation, Infrared Ion Spectroscopy, and Reaction Pathway Calculations.

Science.gov (United States)

Ranka, Karnamohit; Zhao, Ning; Yu, Long; Stanton, John F; Polfer, Nicolas C

2018-05-29

We report on the ultraviolet photodissociation (UVPD) chemistry of protonated tyrosine, iodotyrosine, and diiodotyrosine. Distonic loss of the iodine creates a high-energy radical at the aromatic ring that engages in hydrogen/proton rearrangement chemistry. Based on UVPD kinetics measurements, the appearance of this radical is coincident with the UV irradiation pulse (8 ns). Conversely, sequential UVPD product ions exhibit metastable decay on ca. 100 ns timescales. Infrared ion spectroscopy is capable of confirming putative structures of the rearrangement products as proton transfers from the imine and β-carbon hydrogens. Potential energy surfaces for the various reaction pathways indicate that the rearrangement chemistry is highly complex, compatible with a cascade of rearrangements, and that there is no preferred rearrangement pathway even in small molecular systems like these. Graphical Abstract.

Moving from local to State water governance to resolve a local conflict between irrigated agriculture and commercial forestry in South Australia

Science.gov (United States)

Gillet, Virginie; McKay, Jennifer; Keremane, Ganesh

2014-11-01

In the Lower Limestone Coast, South Australia, a unique water allocation plan has been under consideration for several years. This plan is the first in Australia to consider forestry as a water affecting activity. Indeed, forestry plantations have a twofold impact on water-rainfall or aquifer recharge interception and direct extraction of groundwater in shallow water table areas-and alter the available water for irrigation as a result of the previous water budget. This paper examines how water is allocated across the competing requirements for water but also across the competing legal, economic and administrative scales embodied by the competing water users; and thus it also details the pre-judicial mechanism used to resolve the conflict over these competing scales. Qualitative and quantitative content analysis in Nvivo was applied to: (i) 180 local newspaper articles on the planning process, (ii) 65 submission forms filled in by the community during a public consultation on the draft water plan and (iii) 20 face-to-face interviews of keys stakeholders involved in the planning process. The social sustainability perspective taken in this study establishes the legal, economic and administrative competitive scales at stake in the conflict regarding water between forestry and irrigation. It also evidences the special feature of this paper, which is that to overcome these competitions and resolve the local conflict before judicial process, the water governance moved up in the administrative scale, from local/regional to State level. Initiated and initially prepared at regional level through the local Natural Resources Management Board, the water planning process was taken up to State level through the formation of an Interdepartmental Committee and the establishment of a Taskforce in charge of developing a policy. These were supported by an amendment of a State legislation on Natural Resources Management to manage the water impacts of forestry plantations.

The dependence of the ultrafast relaxation kinetics of the S2 and S1 states in β-carotene homologs and lycopene on conjugation length studied by femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies

Science.gov (United States)

Kosumi, Daisuke; Fujiwara, Masazumi; Fujii, Ritsuko; Cogdell, Richard J.; Hashimoto, Hideki; Yoshizawa, Masayuki

2009-06-01

The ultrafast relaxation kinetics of all-trans-β-carotene homologs with varying numbers of conjugated double bonds n(n =7-15) and lycopene (n =11) has been investigated using femtosecond time-resolved absorption and Kerr-gate fluorescence spectroscopies, both carried out under identical excitation conditions. The nonradiative relaxation rates of the optically allowed S2(1Bu+1) state were precisely determined by the time-resolved fluorescence. The kinetics of the optically forbidden S1(2Ag-1) state were observed by the time-resolved absorption measurements. The dependence of the S1 relaxation rates upon the conjugation length is adequately described by application of the energy gap law. In contrast to this, the nonradiative relaxation rates of S2 have a minimum at n =9 and show a reverse energy gap law dependence for values of n above 11. This anomalous behavior of the S2 relaxation rates can be explained by the presence of an intermediate state (here called the Sx state) located between the S2 and S1 states at large values of n (such as n =11). The presence of such an intermediate state would then result in the following sequential relaxation pathway S2→Sx→S1→S0. A model based on conical intersections between the potential energy curves of these excited singlet states can readily explain the measured relationships between the decay rates and the energy gaps.

Photoelectron and photodissociation studies of free atoms and molecules, using synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Medhurst, Laura Jane [Univ. of California, Berkeley, CA (United States)

1991-11-01

High resolution synchrotron radiation and Zero-Kinetic-Energy Photoelectron spectroscopy were used to study two-electron transitions in atomic systems at their ionization thresholds. Using this same technique the core-ionized mainline and satellite states of N₂ and CO were studied with vibrational resolution. Vibrationally resolved synchrotron radiation was used to study the dissociation of N₂, C₂H₄, and CH₃Cl near the N 1s and C 1s thresholds. The photoelectron satellites of the argon 3s, krypton 4s and xenon 4d subshells were studied with zero kinetic energy photoelectron spectroscopy at their ionization thresholds. In all of these cases, satellites with lower binding energies are enhanced at their thresholds while those closer to the double ionization threshold are suppressed relative to their intensities at high incident light energies.

Resolvent-based modeling of passive scalar dynamics in wall-bounded turbulence

Science.gov (United States)

Dawson, Scott; Saxton-Fox, Theresa; McKeon, Beverley

2017-11-01

The resolvent formulation of the Navier-Stokes equations expresses the system state as the output of a linear (resolvent) operator acting upon a nonlinear forcing. Previous studies have demonstrated that a low-rank approximation of this linear operator predicts many known features of incompressible wall-bounded turbulence. In this work, this resolvent model for wall-bounded turbulence is extended to include a passive scalar field. This formulation allows for a number of additional simplifications that reduce model complexity. Firstly, it is shown that the effect of changing scalar diffusivity can be approximated through a transformation of spatial wavenumbers and temporal frequencies. Secondly, passive scalar dynamics may be studied through the low-rank approximation of a passive scalar resolvent operator, which is decoupled from velocity response modes. Thirdly, this passive scalar resolvent operator is amenable to approximation by semi-analytic methods. We investigate the extent to which this resulting hierarchy of models can describe and predict passive scalar dynamics and statistics in wall-bounded turbulence. The support of AFOSR under Grant Numbers FA9550-16-1-0232 and FA9550-16-1-0361 is gratefully acknowledged.

Ultrafast time-resolved spectroscopy of lead halide perovskite films

Science.gov (United States)

Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

2015-09-01

Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

Raman spectrum of predissociating H/sub 2/S

International Nuclear Information System (INIS)

Kleinermanns, K.; Suntz, R.; Schneider, R.

1986-01-01

Emission spectroscopy of photodissociating molecules provides interesting insights into the short-time dynamics of bond raptures. The authors report here a resolved H/sub 2/S photoemission spectrum after excitation at 193 nm, although its electronic spectrum in this wavelength region is diffuse. The electronic spectrum of H/sub 2/S between 250 and 170 nm is nearly continuous probably due to predissociation

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.

Three-body dissociations: The photodissociation of dimethyl sulfoxide at 193 nm

Energy Technology Data Exchange (ETDEWEB)

Blank, D.A.; North, S.W.; Stranges, D. [Lawrence Berkeley National Lab., CA (United States)] [and others

1997-04-01

When a molecule with two equivalent chemical bonds is excited above the threshold for dissociation of both bonds, how the rupture of the two bonds is temporally coupled becomes a salient question. Following absorption at 193 nm dimethyl sulfoxide (CH{sub 3}SOCH{sub 3}) contains enough energy to rupture both C-S bonds. This can happen in a stepwise (reaction 1) or concerted (reaction 2) fashion where the authors use rotation of the SOCH{sub 3} intermediate prior to dissociation to define a stepwise dissociation: (1) CH{sub 3}SOCH{sub 3} {r_arrow} 2CH{sub 3} + SO; (2a) CH{sub 3}SOCH{sub 3} {r_arrow} CH{sub 3} + SOCH{sub 3}; and (2b) SOCH{sub 3} {r_arrow} SO + CH{sub 3}. Recently, the dissociation of dimethyl sulfoxide following absorption at 193 nm was suggested to involve simultaneous cleavage of both C-S bonds on an excited electronic surface. This conclusion was inferred from laser induced fluorescence (LIF) and resonant multiphoton ionization (2+1 REMPI) measurements of the internal energy content in the CH{sub 3} and SO photoproducts and a near unity quantum yield measured for SO. Since this type of concerted three body dissociation is very interesting and a rather rare event in photodissociation dynamics, the authors chose to investigate this system using the technique of photofragment translational spectroscopy at beamline 9.0.2.1. The soft photoionization provided by the VUV undulator radiation allowed the authors to probe the SOCH{sub 3} intermediate which had not been previously observed and provided good evidence that the dissociation of dimethyl sulfoxide primarily proceeds via a two step dissociation, reaction 2.

Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Huse, Nils; Kim, Tae Kyu; Jamula, Lindsey; McCusker, James K.; de Groot, Frank M. F.; Schoenlein, Robert W.

2010-04-30

Solution-phase photoinduced low-spin to high-spin conversion in the FeII polypyridyl complex [Fe(tren(py)3)]2+ (where tren(py)3 is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following 1A1 --> 1MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L2- and L3-edges were observed concomitant with formation of the transient high-spin 5T2 state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 Angstrom increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.

Depth-Resolved Composition and Electronic Structure of Buried Layers and Interfaces in a LaNiO{sub 3}/SrTiO{sub 3} Superlattice from Soft- and Hard- X-ray Standing-Wave Angle-Resolved Photoemission

Energy Technology Data Exchange (ETDEWEB)

Eiteneer, D. [Department of Physics, University of California, Davis, California 95616 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Pálsson, G.K., E-mail: gunnar.palsson@physics.uu.se [Department of Physics, University of California, Davis, California 95616 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Nemšák, S. [Department of Physics, University of California, Davis, California 95616 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Peter-Grünberg-Institut PGI-6, Forschungszentrum Julich, 52425 Julich (Germany); Gray, A.X. [Department of Physics, University of California, Davis, California 95616 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States); Kaiser, A.M. [Department of Physics, University of California, Davis, California 95616 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Son, J.; LeBeau, J. [Materials Department, University of California, Santa Barbara, California 93106 (United States); Conti, G. [Department of Physics, University of California, Davis, California 95616 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); and others

2016-08-15

Highlights: • Depth resolved electronic structure of LaNiO{sub 3}/SrTiO{sub 3} superlattices is measured. • The structure is determined by x-ray standing wave angle-resolved photoemission. • Similarity to the electronic structure of La{sub 0.7}Sr{sub 0.3}MnO{sub 3}/SrTiO{sub 3} is discussed. - Abstract: LaNiO{sub 3} (LNO) is an intriguing member of the rare-earth nickelates in exhibiting a metal-insulator transition for a critical film thickness of about 4 unit cells [Son et al., Appl. Phys. Lett. 96, 062114 (2010)]; however, such thin films also show a transition to a metallic state in superlattices with SrTiO{sub 3} (STO) [Son et al., Appl. Phys. Lett. 97, 202109 (2010)]. In order to better understand this transition, we have studied a strained LNO/STO superlattice with 10 repeats of [4 unit-cell LNO/3 unit-cell STO] grown on an (LaAlO{sub 3}){sub 0.3}(Sr{sub 2}AlTaO{sub 6}){sub 0.7} substrate using soft x-ray standing-wave-excited angle-resolved photoemission (SWARPES), together with soft- and hard- x-ray photoemission measurements of core levels and densities-of-states valence spectra. The experimental results are compared with state-of-the-art density functional theory (DFT) calculations of band structures and densities of states. Using core-level rocking curves and x-ray optical modeling to assess the position of the standing wave, SWARPES measurements are carried out for various incidence angles and used to determine interface-specific changes in momentum-resolved electronic structure. We further show that the momentum-resolved behavior of the Ni 3d e{sub g} and t{sub 2g} states near the Fermi level, as well as those at the bottom of the valence bands, is very similar to recently published SWARPES results for a related La{sub 0.7}Sr{sub 0.3}MnO{sub 3}/SrTiO{sub 3} superlattice that was studied using the same technique (Gray et al., Europhysics Letters 104, 17004 (2013)), which further validates this experimental approach and our conclusions. Our

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.

Femtosecond time-resolved hot carrier energy distributions of photoexcited semiconductor quantum dots

International Nuclear Information System (INIS)

Chuang, Chi-Hung; Burda, Clemens; Chen, Xiaobo

2013-01-01

Using femtosecond transient absorption spectroscopy, we investigated hot carrier distributions in semiconductor cadmium selenide quantum dots. The relaxation processes represent the behavior of an ensemble of QDs. This concept is applied for analysis with the Fermi-Dirac distribution and relaxation processes among different electron-hole pair states. By extracting the experimental hot carrier distribution and fitting with the Fermi-Dirac function, we resolved the rapid thermalization processes, such as carrier-carrier and carrier-phonon interactions was resolved within one picosecond upon photoexcitation. The analysis, using the Fermi-Dirac distribution modulated by the density of states, provides a general route to understanding the carrier cooling and heat dissipation processes in quantum dot-based systems. (copyright 2012 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

Science.gov (United States)

Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; Glover, William J.; Mori, Toshifumi; Schultz, Thomas; Schuurman, Michael S.; Martínez, Todd J.; Stolow, Albert

2018-04-01

The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1Bu (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans' correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us to report the direct observation of the famously elusive S1(21Ag) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 11Bu and 21Ag states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S2(11Bu) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1Bu surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. In Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.

Time-resolved wave profile measurements in copper to Megabar pressures

Energy Technology Data Exchange (ETDEWEB)

Chhabildas, L C; Asay, J R

1981-01-01

Many time-resolved techniques have been developed which have greatly aided in the understanding of dynamic material behavior such as the high pressure-dynamic strength of materials. In the paper, time-resolved measurements of copper (at shock-induced high pressures and temperatures) are used to illustrate the capability of using such techniques to investigate high pressure strength. Continuous shock loading and release wave profiles have been made in copper to 93 GPa using velocity interferometric techniques. Fine structure in the release wave profiles from the shocked state indicates an increase in shear strength of copper to 1.5 GPa at 93 GPa from its ambient value of 0.08 GPa.

Spectrum of Slip Processes on the Subduction Interface in a Continuum Framework Resolved by Rate-and State Dependent Friction and Adaptive Time Stepping

Science.gov (United States)

Herrendoerfer, R.; van Dinther, Y.; Gerya, T.

2015-12-01

To explore the relationships between subduction dynamics and the megathrust earthquake potential, we have recently developed a numerical model that bridges the gap between processes on geodynamic and earthquake cycle time scales. In a self-consistent, continuum-based framework including a visco-elasto-plastic constitutive relationship, cycles of megathrust earthquake-like ruptures were simulated through a purely slip rate-dependent friction, albeit with very low slip rates (van Dinther et al., JGR, 2013). In addition to much faster earthquakes, a range of aseismic slip processes operate at different time scales in nature. These aseismic processes likely accommodate a considerable amount of the plate convergence and are thus relevant in order to estimate the long-term seismic coupling and related hazard in subduction zones. To simulate and resolve this wide spectrum of slip processes, we innovatively implemented rate-and state dependent friction (RSF) and an adaptive time-stepping into our continuum framework. The RSF formulation, in contrast to our previous friction formulation, takes the dependency of frictional strength on a state variable into account. It thereby allows for continuous plastic yielding inside rate-weakening regions, which leads to aseismic slip. In contrast to the conventional RSF formulation, we relate slip velocities to strain rates and use an invariant formulation. Thus we do not require the a priori definition of infinitely thin, planar faults in a homogeneous elastic medium. With this new implementation of RSF, we succeed to produce consistent cycles of frictional instabilities. By changing the frictional parameter a, b, and the characteristic slip distance, we observe a transition from stable sliding to stick-slip behaviour. This transition is in general agreement with predictions from theoretical estimates of the nucleation size, thereby to first order validating our implementation. By incorporating adaptive time-stepping based on a

Differential Fragmentation of Mobility-Selected Glycans via Ultraviolet Photodissociation and Ion Mobility-Mass Spectrometry

Science.gov (United States)

Morrison, Kelsey A.; Clowers, Brian H.

2017-06-01

The alternative dissociation pathways initiated by ultraviolet photodissociation (UVPD) compared with collision-induced dissociation (CID) may provide useful diagnostic fragments for biomolecule identification, including glycans. However, underivatized glycans do not commonly demonstrate strong UV absorbance, resulting in low fragmentation yields for UVPD spectra. In contrast to UVPD experiments that leverage covalent modification of glycans, we detail the capacity of metal adduction to yield comparatively rich UVPD fragmentation patterns and enhance separation factors for an isomeric glycan set in a drift tube ion mobility system. Ion mobility and UVPD-MS spectra for two N-acetyl glycan isomers were examined, each adducted with sodium or cobalt cations, with the latter providing fragment yield gains of an order of magnitude versus sodium adducts. Furthermore, our glycan analysis incorporated front-end ion mobility separation such that the structural glycan isomers could still be identified even as a mixture and not simply composite spectra of isomeric standards. Cobalt adduction proved influential in the glycan separation by yielding an isomer resolution of 0.78 when analyzed simultaneously versus no discernable separation obtained with the sodium adducts. It is the combined enhancement of both isomeric drift time separation and isomer distinction with improved UVPD fragment ion yields that further bolster multivalent metal adduction for advancing glycan IM-MS experiments. [Figure not available: see fulltext.

Photodissociation dynamics of propene at 157.6 nm: Kinetic energy distributions and branching ratios

International Nuclear Information System (INIS)

Lee, S.-H.; Lee, Y.-Y.; Lee, Yuan T.; Yang Xueming

2003-01-01

Photodissociation dynamics of propene at 157.6 nm has been investigated in a molecular beam apparatus using the photofragment translational spectroscopic technique combined with the vacuum ultraviolet ionization method. Eleven photofragments have been successfully detected and ascribed to eight (five binary and three triple) dissociation channels: namely, C 3 H 5 +H, C 3 H 4 +H+H, C 3 H 4 +H 2 , C 3 H 3 +H 2 +H, C 2 H 4 +CH 2 , C 2 H 3 +CH 3 , C 2 H 2 +CH 4 , and C 2 H 2 +CH 3 +H. Their branching ratios have been determined to be 1%, 7%, 2 H 2 +CH 3 +H channel. In addition, the averaged kinetic energy releases and the fractions in translational energy have also been determined from the measured kinetic energy distributions. For the binary dissociation channels, the fractions in translational energy are less than 18% except the C 3 H 5 +H channel, whereas they are more than 42% for the triple dissociation channels. An intriguing finding indicates that the C 2 H 4 +CH 2 channel has a nearly identical kinetic energy distribution and a similar branching ratio to the C 2 H 3 +CH 3 channel, although the former undergoes a three-center elimination process different from the C-C bond rupture occurring in the latter

The role of spin-orbit coupling in the photolysis of methylcobalamin

Energy Technology Data Exchange (ETDEWEB)

Andruniów, Tadeusz [Department of Chemistry, Advanced Materials Engineering and Modelling Group, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Lodowski, Piotr; Jaworska, Maria [Department of Theoretical Chemistry, Institute of Chemistry, University of Silesia, Szkolna 9, PL-40 006 Katowice (Poland); Garabato, Brady D. [Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292 (United States); Kozlowski, Pawel M., E-mail: pawel@louisville.edu [Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292 (United States); Department of Food Sciences, Medical University of Gdansk, Al. Gen. J. Hallera 107, 80-416 Gdansk (Poland)

2016-03-28

The photolysis of the methylcobalamin cofactor (MeCbl) in its base-off form was investigated by considering the extent of spin-orbit coupling (SOC). Triplet Co–C photodissociation pathways previously invoked at the density functional theory level using Landau-Zener theory were further validated with ab initio calculations that combine SOC based on multi-state second order perturbation theory. It was determined that SOC is feasible between singlet and triplet states at elongated Co–C distances, leading to photodissociation from the state having dominant σ(d{sub z}{sup 2}) character, by either direct coupling with the lowest singlet states or by crossing with SOC mixed triplets.

Time-resolved photoelectron spectroscopy of nitrobenzene and its aldehydes

Science.gov (United States)

Schalk, Oliver; Townsend, Dave; Wolf, Thomas J. A.; Holland, David M. P.; Boguslavskiy, Andrey E.; Szöri, Milan; Stolow, Albert

2018-01-01

We report the first femtosecond time-resolved photoelectron spectroscopy study of 2-, 3- and 4-nitrobenzaldehyde (NBA) and nitrobenzene (NBE) in the gas phase upon excitation at 200 nm. In 3- and 4-NBA, the dynamics follow fast intersystem crossing within 1-2 picoseconds. In 2-NBA and NBE, the dynamics are faster (∼ 0.5 ps). 2-NBA undergoes hydrogen transfer similar to solution phase dynamics. NBE either releases NO2 in the excited state or converts internally back to the ground state. We discuss why these channels are suppressed in the other nitrobenzaldehydes.

Thermally activated delayed fluorescence of fluorescein derivative for time-resolved and confocal fluorescence imaging.

Science.gov (United States)

Xiong, Xiaoqing; Song, Fengling; Wang, Jingyun; Zhang, Yukang; Xue, Yingying; Sun, Liangliang; Jiang, Na; Gao, Pan; Tian, Lu; Peng, Xiaojun

2014-07-09

Compared with fluorescence imaging utilizing fluorophores whose lifetimes are in the order of nanoseconds, time-resolved fluorescence microscopy has more advantages in monitoring target fluorescence. In this work, compound DCF-MPYM, which is based on a fluorescein derivative, showed long-lived luminescence (22.11 μs in deaerated ethanol) and was used in time-resolved fluorescence imaging in living cells. Both nanosecond time-resolved transient difference absorption spectra and time-correlated single-photon counting (TCSPC) were employed to explain the long lifetime of the compound, which is rare in pure organic fluorophores without rare earth metals and heavy atoms. A mechanism of thermally activated delayed fluorescence (TADF) that considers the long wavelength fluorescence, large Stokes shift, and long-lived triplet state of DCF-MPYM was proposed. The energy gap (ΔEST) of DCF-MPYM between the singlet and triplet state was determined to be 28.36 meV by the decay rate of DF as a function of temperature. The ΔE(ST) was small enough to allow efficient intersystem crossing (ISC) and reverse ISC, leading to efficient TADF at room temperature. The straightforward synthesis of DCF-MPYM and wide availability of its starting materials contribute to the excellent potential of the compound to replace luminescent lanthanide complexes in future time-resolved imaging technologies.

Angle-resolved effective potentials for disk-shaped molecules

Energy Technology Data Exchange (ETDEWEB)

Heinemann, Thomas, E-mail: thomas.heinemann@tu-berlin.de; Klapp, Sabine H. L., E-mail: klapp@physik.tu-berlin.de [Institut für Theoretische Physik, Technische Universität Berlin, Hardenbergstr. 36, 10623 Berlin (Germany); Palczynski, Karol, E-mail: karol.palczynski@helmholtz-berlin.de; Dzubiella, Joachim, E-mail: joachim.dzubiella@helmholtz-berlin.de [Institut für Physik, Humboldt Universität zu Berlin, Newtonstraße 15, 12489 Berlin (Germany); Helmholtz Zentrum Berlin (HZB), Institute of Soft Matter and Functional Materials, Hahn-Meitner Platz 1, 14109 Berlin (Germany)

2014-12-07

We present an approach for calculating coarse-grained angle-resolved effective pair potentials for uniaxial molecules. For integrating out the intramolecular degrees of freedom we apply umbrella sampling and steered dynamics techniques in atomistically-resolved molecular dynamics (MD) computer simulations. Throughout this study we focus on disk-like molecules such as coronene. To develop the methods we focus on integrating out the van der Waals and intramolecular interactions, while electrostatic charge contributions are neglected. The resulting coarse-grained pair potential reveals a strong temperature and angle dependence. In the next step we fit the numerical data with various Gay-Berne-like potentials to be used in more efficient simulations on larger scales. The quality of the resulting coarse-grained results is evaluated by comparing their pair and many-body structure as well as some thermodynamic quantities self-consistently to the outcome of atomistic MD simulations of many-particle systems. We find that angle-resolved potentials are essential not only to accurately describe crystal structures but also for fluid systems where simple isotropic potentials start to fail already for low to moderate packing fractions. Further, in describing these states it is crucial to take into account the pronounced temperature dependence arising in selected pair configurations due to bending fluctuations.

Time- and Site-Resolved Dynamics in a Topological Circuit

Directory of Open Access Journals (Sweden)

Jia Ningyuan

2015-06-01

Full Text Available From studies of exotic quantum many-body phenomena to applications in spintronics and quantum information processing, topological materials are poised to revolutionize the condensed-matter frontier and the landscape of modern materials science. Accordingly, there is a broad effort to realize topologically nontrivial electronic and photonic materials for fundamental science as well as practical applications. In this work, we demonstrate the first simultaneous site- and time-resolved measurements of a time-reversal-invariant topological band structure, which we realize in a radio-frequency photonic circuit. We control band-structure topology via local permutation of a traveling-wave capacitor-inductor network, increasing robustness by going beyond the tight-binding limit. We observe a gapped density of states consistent with a modified Hofstadter spectrum at a flux per plaquette of ϕ=π/2. In situ probes of the band gaps reveal spatially localized bulk states and delocalized edge states. Time-resolved measurements reveal dynamical separation of localized edge excitations into spin-polarized currents. The radio-frequency circuit paradigm is naturally compatible with nonlocal coupling schemes, allowing us to implement a Möbius strip topology inaccessible in conventional systems. This room-temperature experiment illuminates the origins of topology in band structure, and when combined with circuit quantum electrodynamics techniques, it provides a direct path to topologically ordered quantum matter.

Time-resolved x-ray laser induced photoelectron spectroscopy of isochoric heated copper

International Nuclear Information System (INIS)

Nelson, A.J.; Dunn, J.; Hunter, J.; Widmann, K.

2005-01-01

Time-resolved x-ray photoelectron spectroscopy is used to probe the nonsteady-state evolution of the valence band electronic structure of laser heated ultrathin (50 nm) copper. A metastable phase is studied using a 527 nm wavelength 400 fs laser pulse containing 0.1-2.5 mJ laser energy focused in a large 500x700 μm 2 spot to create heated conditions of 0.07-1.8x10 12 W cm -2 intensity. Valence band photoemission spectra are presented showing the changing occupancy of the Cu 3d level with heating are presented. These picosecond x-ray laser induced time-resolved photoemission spectra of laser-heated ultrathin Cu foil show dynamic changes in the electronic structure. The ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials

Intrinsic spin polarized electronic structure of CrO2 epitaxial film revealed by bulk-sensitive spin-resolved photoemission spectroscopy

International Nuclear Information System (INIS)

Fujiwara, Hirokazu; Sunagawa, Masanori; Kittaka, Tomoko; Terashima, Kensei; Wakita, Takanori; Muraoka, Yuji; Yokoya, Takayoshi

2015-01-01

We have performed bulk-sensitive spin-resolved photoemission spectroscopy in order to clarify the intrinsic spin-resolved electronic states of half-metallic ferromagnet CrO 2 . We used CrO 2 epitaxial films on TiO 2 (100), which shows a peak at 1 eV with a clear Fermi edge, consistent with the bulk-sensitive PES spectrum for CrO 2 . In spin-resolved spectra at 40 K, while the Fermi edge was observed in the spin up (majority spin) state, no states at the Fermi level (E F ) with an energy gap of 0.5 eV below E F were observed in the spin down (minority spin) state. At 300 K, the gap in the spin down state closes. These results are consistent with resistivity measurements and magnetic hysteresis curves of the fabricated CrO 2 film, constituting spectroscopic evidence for the half-metallicity of CrO 2 at low temperature and reducing the spin polarization at room temperature. We also discuss the electron correlation effects of Cr 3d

Time-resolved studies

International Nuclear Information System (INIS)

Mills, D.M.

1992-01-01

When new or more powerful probes become available that offer both shorter data-collection times and the opportunity to apply innovative approaches to established techniques, it is natural that investigators consider the feasibility of exploring the kinetics of time-evolving systems. This stimulating area of research not only can lead to insights into the metastable or excited states that a system may populate on its way to a ground state, but can also lead to a better understanding of that final state. Synchrotron radiation, with its unique properties, offers just such a tool to extend X-ray measurements from the static to the time-resolved regime. The most straight-forward application of synchrotron radiation to the study of transient phenomena is directly through the possibility of decreased data-collection times via the enormous increase in flux over that of a laboratory X-ray system. Even further increases in intensity can be obtained through the use of novel X-ray optical devices. Widebandpass monochromators, e.g., that utilize the continuous spectral distribution of synchrotron radiation, can increase flux on the sample several orders of magnitude over conventional X-ray optical systems thereby allowing a further shortening of the data-collection time. Another approach that uses the continuous spectral nature of synchrotron radiation to decrease data-collection times is the open-quote parallel data collectionclose quotes method. Using this technique, intensities as a function of X-ray energy are recorded simultaneously for all energies rather than sequentially recording data at each energy, allowing for a dramatic decrease in the data-collection time

In-pile Thermal Conductivity Characterization with Time Resolved Raman

Energy Technology Data Exchange (ETDEWEB)

Wang, Xinwei [Iowa State Univ., Ames, IA (United States). Dept. of Mechanical Engineering; Hurley, David H. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2018-03-19

The project is designed to achieve three objectives: (1) Develop a novel time resolved Raman technology for direct measurement of fuel and cladding thermal conductivity. (2) Validate and improve the technology development by measuring ceramic materials germane to the nuclear industry. (3) Conduct instrumentation development to integrate optical fiber into our sensing system for eventual in-pile measurement. We have developed three new techniques: time-domain differential Raman (TD-Raman), frequency-resolved Raman (FR-Raman), and energy transport state-resolved Raman (ET-Raman). The TD-Raman varies the laser heating time and does simultaneous Raman thermal probing, the FR-Raman probes the material’s thermal response under periodical laser heating of different frequencies, and the ET-Raman probes the thermal response under steady and pulsed laser heating. The measurement capacity of these techniques have been fully assessed and verified by measuring micro/nanoscale materials. All these techniques do not need the data of laser absorption and absolute material temperature rise, yet still be able to measure the thermal conductivity and thermal diffusivity with unprecedented accuracy. It is expected they will have broad applications for in-pile thermal characterization of nuclear materials based on pure optical heating and sensing.

Sources and mixing state of size-resolved elemental carbon particles in a European megacity: Paris

Science.gov (United States)

Healy, R. M.; Sciare, J.; Poulain, L.; Kamili, K.; Merkel, M.; Müller, T.; Wiedensohler, A.; Eckhardt, S.; Stohl, A.; Sarda-Estève, R.; McGillicuddy, E.; O'Connor, I. P.; Sodeau, J. R.; Wenger, J. C.

2012-02-01

compared with 85% and 15% respectively for BC estimated from the aethalometer model. On average, the mass size distribution for EC particles is bimodal; the smaller mode is attributed to locally emitted, mostly externally mixed EC particles, while the larger mode is dominated by aged, internally mixed ECOCNOx particles associated with continental transport events. Periods of continental influence were identified using the Lagrangian Particle Dispersion Model (LPDM) "FLEXPART". A consistent minimum between the two EC mass size modes was observed at approximately 400 nm for the measurement period. EC particles below this size are attributed to local emissions using chemical mixing state information and contribute 79% of the scaled ATOFMS EC particle mass, while particles above this size are attributed to continental transport events and contribute 21% of the EC particle mass. These results clearly demonstrate the potential benefit of monitoring size-resolved mass concentrations for the separation of local and continental EC emissions. Knowledge of the relative input of these emissions is essential for assessing the effectiveness of local abatement strategies.

Photoneutron cross sections for D2O and beryllium

International Nuclear Information System (INIS)

Bowsher, H.F.; Woods, F.J.; Baumann, N.P.

1975-01-01

The photodissociation cross section by 24 Na gamma rays was measured for deuterium in order to resolve a discrepancy between earlier measurements (1.43 to 1.59 millibarns) and a more recently reported one (1.34 mb). The measurement of the beryllium (γ,n) cross section for 24 Na gamma rays was also included as a check. Results for deuterium (1.54 mb) are in agreement with the earlier values

Time resolved resonant inelastic X-ray scattering: A supreme tool to understand dynamics in solids and molecules

International Nuclear Information System (INIS)

Beye, M.; Wernet, Ph.; Schüßler-Langeheine, C.; Föhlisch, A.

2013-01-01

Highlights: •The high specificity of RIXS ideally suits time-resolved measurements. •Methods relating to the core hole lifetime cover the low femtosecond regime. •Pump-probe methods are used starting at sub-ps time scales. •FELs and synchrotrons are useful for pump-probe studies. •Examples from solid state dynamics and molecules are discussed. -- Abstract: Dynamics in materials typically involve different degrees of freedom, like charge, lattice, orbital and spin in a complex interplay. Time-resolved resonant inelastic X-ray scattering (RIXS) as a highly selective tool can provide unique insight and follow the details of dynamical processes while resolving symmetries, chemical and charge states, momenta, spin configurations, etc. In this paper, we review examples where the intrinsic scattering duration time is used to study femtosecond phenomena. Free-electron lasers access timescales starting in the sub-ps range through pump-probe methods and synchrotrons study the time scales longer than tens of ps. In these examples, time-resolved resonant inelastic X-ray scattering is applied to solids as well as molecular systems

Photosensitized production of singlet oxygen: spatially-resolved optical studies in single cells

DEFF Research Database (Denmark)

Breitenbach, Thomas; Kuimova, Marina; Gbur, Peter

2009-01-01

be monitored using viability assays. Time- and spatially-resolved optical measurements of both singlet oxygen and its precursor, the excited state sensitizer, reflect the complex and dynamic morphology of the cell. These experiments help elucidate photoinduced, oxygen-dependent events that compromise cell...

Developments in time-resolved high pressure x-ray diffraction using rapid compression and decompression

International Nuclear Information System (INIS)

Smith, Jesse S.; Sinogeikin, Stanislav V.; Lin, Chuanlong; Rod, Eric; Bai, Ligang; Shen, Guoyin

2015-01-01

Complementary advances in high pressure research apparatus and techniques make it possible to carry out time-resolved high pressure research using what would customarily be considered static high pressure apparatus. This work specifically explores time-resolved high pressure x-ray diffraction with rapid compression and/or decompression of a sample in a diamond anvil cell. Key aspects of the synchrotron beamline and ancillary equipment are presented, including source considerations, rapid (de)compression apparatus, high frequency imaging detectors, and software suitable for processing large volumes of data. A number of examples are presented, including fast equation of state measurements, compression rate dependent synthesis of metastable states in silicon and germanium, and ultrahigh compression rates using a piezoelectric driven diamond anvil cell

Getting the job done: Resolving state-federal conflicts in Superfund

Energy Technology Data Exchange (ETDEWEB)

Smith, R.; Silver, D.

1998-12-31

The American system of federalism creates frequent opportunities for clashes between state and federal environmental regulators.State and federal environmental laws overlap but are not easily reconciled. Most federal environmental law provides no clear answer as to how to reconcile differing mandates of state and federal environmental regulators. In this article, they will examine these state-federal conflicts as they played out in 1994 in the cleanup of contaminated sites in the state of Washington. This article describes the way a regional office of the Environmental Protection Agency and the state`s Department of Ecology developed a novel approach to managing the essential tension between overlapping state and federal cleanup laws.

Time-Resolved Diffuse Optical Spectroscopy and Imaging Using Solid-State Detectors: Characteristics, Present Status, and Research Challenges.

Science.gov (United States)

Alayed, Mrwan; Deen, M Jamal

2017-09-14

Diffuse optical spectroscopy (DOS) and diffuse optical imaging (DOI) are emerging non-invasive imaging modalities that have wide spread potential applications in many fields, particularly for structural and functional imaging in medicine. In this article, we review time-resolved diffuse optical imaging (TR-DOI) systems using solid-state detectors with a special focus on Single-Photon Avalanche Diodes (SPADs) and Silicon Photomultipliers (SiPMs). These TR-DOI systems can be categorized into two types based on the operation mode of the detector (free-running or time-gated). For the TR-DOI prototypes, the physical concepts, main components, figures-of-merit of detectors, and evaluation parameters are described. The performance of TR-DOI prototypes is evaluated according to the parameters used in common protocols to test DOI systems particularly basic instrumental performance (BIP). In addition, the potential features of SPADs and SiPMs to improve TR-DOI systems and expand their applications in the foreseeable future are discussed. Lastly, research challenges and future developments for TR-DOI are discussed for each component in the prototype separately and also for the entire system.

Interaction of VUV-photons with molecules. Spectroscopy and dynamics of molecular superexcited states

International Nuclear Information System (INIS)

Hatano, Y.

2002-01-01

Complete text of publication follows. A survey is given of recent progress in experimental studies of the interaction of VUV-photons with molecules, i.e., those of photoabsorption, photoionization, and photodissociation of molecules in the excitation photon energy range of 10-50 eV, with a particular emphasis placed on current understanding of the spectroscopy and dynamics of formed molecular superexcited states. These studies are of great importance in understanding the interaction of ionizing radiation with matter. Molecules studied are ranged from simple diatomic and triatomic molecules to polyatomic molecules such as hydrocarbons. Most of the observed molecular superexcited states are assigned to high Rydber states which are vibrationally, doubly, or inner-core excited and converge to each of ion states. Non-Rydberg superexcited states are also observed. Dissociation into neutral fragments in comparison with ionization is of unexpectedly great importance in the observed decay of each of these state-assigned superexcited molecules. Dissociation dynamics as well as its products of superexcited states are remarkably different from those of lower excited states below about ionization thresholds. Some remarks are also presented of molecules in the condensed phase

Simulation of angle-resolved photoemission spectra by approximating the final state by a plane wave: From graphene to polycyclic aromatic hydrocarbon molecules

Energy Technology Data Exchange (ETDEWEB)

Puschnig, Peter, E-mail: peter.puschnig@uni-graz.at; Lüftner, Daniel

2015-04-15

Highlights: • Computational study on angular dependent photoemission spectroscopy. • Graphene and polycyclic aromatic hydrocarbon molecules. • Plane wave final state approximation accounts for experimental findings. - Abstract: We present a computational study on the angular-resolved photoemission spectra (ARPES) from a number of polycyclic aromatic hydrocarbons and graphene. Our theoretical approach is based on ab-initio density functional theory and the one-step model where we greatly simplify the evaluation of the matrix element by assuming a plane wave for the final state. Before comparing our ARPES simulations with available experimental data, we discuss how typical approximations for the exchange-correlation energy affect orbital energies. In particular, we show that by employing a hybrid functional, considerable improvement can be obtained over semi-local functionals in terms of band widths and relative energies of π and σ states. Our ARPES simulations for graphene show that the plane wave final state approximation provides indeed an excellent description when compared to experimental band maps and constant binding energy maps. Furthermore, our ARPES simulations for a number of polycyclic aromatic molecules from the oligo-acene, oligo-phenylene, phen-anthrene families as well as for disc-shaped molecules nicely illustrate the evolution of the electronic structure from molecules with increasing size towards graphene.

Sources and mixing state of size-resolved elemental carbon particles in a European megacity: Paris

Directory of Open Access Journals (Sweden)

R. M. Healy

2012-02-01

mass was apportioned to fossil fuel and biomass burning respectively using the ATOFMS data compared with 85% and 15% respectively for BC estimated from the aethalometer model. On average, the mass size distribution for EC particles is bimodal; the smaller mode is attributed to locally emitted, mostly externally mixed EC particles, while the larger mode is dominated by aged, internally mixed ECOCNO_x particles associated with continental transport events. Periods of continental influence were identified using the Lagrangian Particle Dispersion Model (LPDM "FLEXPART". A consistent minimum between the two EC mass size modes was observed at approximately 400 nm for the measurement period. EC particles below this size are attributed to local emissions using chemical mixing state information and contribute 79% of the scaled ATOFMS EC particle mass, while particles above this size are attributed to continental transport events and contribute 21% of the EC particle mass. These results clearly demonstrate the potential benefit of monitoring size-resolved mass concentrations for the separation of local and continental EC emissions. Knowledge of the relative input of these emissions is essential for assessing the effectiveness of local abatement strategies.

High-resolution spectroscopic probes of collisions and half-collisions

Energy Technology Data Exchange (ETDEWEB)

Hall, G.E. [Brookhaven National Laboratory, Upton, NY (United States)

1993-12-01

Research in this program explores the dynamics of gas phase collisions and photodissociation by high-resolution laser spectroscopy. Simultaneous state and velocity detection frequently permits a determination of scalar or vector correlations among products. The correlated product distributions are always more informative, and often easier to interpret than the uncorrelated product state distributions. The authors have recently built an apparatus to record transient absorption spectra with 50 nS time resolution and 20 MHz frequency resolution using a single frequency Ti:sapphire laser. The photodissociation of NCCN and C{sub 2}H{sub 5}SCN at 193 nm is discussed.

REMOVING BIASES IN RESOLVED STELLAR MASS MAPS OF GALAXY DISKS THROUGH SUCCESSIVE BAYESIAN MARGINALIZATION

Energy Technology Data Exchange (ETDEWEB)

Martínez-García, Eric E. [Cerrada del Rey 40-A, Chimalcoyoc Tlalpan, Ciudad de México, C.P. 14630, México (Mexico); González-Lópezlira, Rosa A.; Bruzual A, Gustavo [Instituto de Radioastronomía y Astrofísica, UNAM, Campus Morelia, Michoacán, C.P. 58089, México (Mexico); Magris C, Gladis, E-mail: martinezgarciaeric@gmail.com [Centro de Investigaciones de Astronomía, Apartado Postal 264, Mérida 5101-A (Venezuela, Bolivarian Republic of)

2017-01-20

Stellar masses of galaxies are frequently obtained by fitting stellar population synthesis models to galaxy photometry or spectra. The state of the art method resolves spatial structures within a galaxy to assess the total stellar mass content. In comparison to unresolved studies, resolved methods yield, on average, higher fractions of stellar mass for galaxies. In this work we improve the current method in order to mitigate a bias related to the resolved spatial distribution derived for the mass. The bias consists in an apparent filamentary mass distribution and a spatial coincidence between mass structures and dust lanes near spiral arms. The improved method is based on iterative Bayesian marginalization, through a new algorithm we have named Bayesian Successive Priors (BSP). We have applied BSP to M51 and to a pilot sample of 90 spiral galaxies from the Ohio State University Bright Spiral Galaxy Survey. By quantitatively comparing both methods, we find that the average fraction of stellar mass missed by unresolved studies is only half what previously thought. In contrast with the previous method, the output BSP mass maps bear a better resemblance to near-infrared images.

Time-resolved fluorescence spectroscopy

International Nuclear Information System (INIS)

Gustavsson, Thomas; Mialocq, Jean-Claude

2007-01-01

This article addresses the evolution in time of light emitted by a molecular system after a brief photo-excitation. The authors first describe fluorescence from a photo-physical point of view and discuss the characterization of the excited state. Then, they explain some basic notions related to fluorescence characterization (lifetime and decays, quantum efficiency, so on). They present the different experimental methods and techniques currently used to study time-resolved fluorescence. They discuss basic notions of time resolution and spectral reconstruction. They briefly present some conventional methods: intensified Ccd cameras, photo-multipliers and photodiodes associated with a fast oscilloscope, and phase modulation. Other methods and techniques are more precisely presented: time-correlated single photon counting (principle, examples, and fluorescence lifetime imagery), streak camera (principle, examples), and optical methods like the Kerr optical effect (principle and examples) and fluorescence up-conversion (principle and theoretical considerations, examples of application)

Time-resolved vibrational spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Tokmakoff, Andrei [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Champion, Paul [Northeastern Univ., Boston, MA (United States); Heilweil, Edwin J. [National Inst. of Standards and Technology (NIST), Boulder, CO (United States); Nelson, Keith A. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ziegler, Larry [Boston Univ., MA (United States)

2009-05-14

This document contains the Proceedings from the 14th International Conference on Time-Resolved Vibrational Spectroscopy, which was held in Meredith, NH from May 9-14, 2009. The study of molecular dynamics in chemical reaction and biological processes using time-resolved spectroscopy plays an important role in our understanding of energy conversion, storage, and utilization problems. Fundamental studies of chemical reactivity, molecular rearrangements, and charge transport are broadly supported by the DOE's Office of Science because of their role in the development of alternative energy sources, the understanding of biological energy conversion processes, the efficient utilization of existing energy resources, and the mitigation of reactive intermediates in radiation chemistry. In addition, time-resolved spectroscopy is central to all fiveof DOE's grand challenges for fundamental energy science. The Time-Resolved Vibrational Spectroscopy conference is organized biennially to bring the leaders in this field from around the globe together with young scientists to discuss the most recent scientific and technological advances. The latest technology in ultrafast infrared, Raman, and terahertz spectroscopy and the scientific advances that these methods enable were covered. Particular emphasis was placed on new experimental methods used to probe molecular dynamics in liquids, solids, interfaces, nanostructured materials, and biomolecules.

Direct observation of spin-resolved full and empty electron states in ferromagnetic surfaces

Energy Technology Data Exchange (ETDEWEB)

Berti, G., E-mail: giulia.berti@polimi.it; Calloni, A.; Brambilla, A.; Bussetti, G.; Duò, L.; Ciccacci, F. [Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133, Milano (Italy)

2014-07-15

We present a versatile apparatus for the study of ferromagnetic surfaces, which combines spin-polarized photoemission and inverse photoemission spectroscopies. Samples can be grown by molecular beam epitaxy and analyzed in situ. Spin-resolved photoemission spectroscopy analysis is done with a hemispherical electron analyzer coupled to a 25 kV-Mott detector. Inverse photoemission spectroscopy experiments are performed with GaAs crystals as spin-polarized electron sources and a UV bandpass photon detector. As an example, measurements on the oxygen passivated Fe(100)-p(1×1)O surface are presented.

Ultrafast measurements of chlorine dioxide photochemistry

Energy Technology Data Exchange (ETDEWEB)

Ludowise, P.D.

1997-08-01

Time-resolved mass spectrometry and time-resolved photoelectron spectroscopy are used to study the ultrafast photodissociation dynamics of chlorine dioxide, an important constituent in stratospheric ozone depletion. Chapter 1 introduces these pump/probe techniques, in which a femtosecond pump pulse excites a molecule to a dissociative state. At a later time, a second femtosecond probe pulse ionizes the molecule. The resulting mass and photoelectron spectra are acquired as a function of the delay between the pump and probe pulses, which follows the evolution of the molecule on the excited state. A comparison to other techniques used to study reaction dynamics is discussed. Chapter 2 includes a detailed description of the design and construction of the experimental apparatus, which consists of a femtosecond laser system, a molecular beam time-of-flight spectrometer, and a data acquisition system. The time-of-flight spectrometer is specifically designed to have a short flight distance to maximize the photoelectron collection efficiency without degrading the resolution, which is limited by the bandwidth of the femtosecond laser system. Typical performance of the apparatus is demonstrated in a study of the time-resolved photoelectron spectroscopy of nitric oxide. The results of the time-resolved mass spectrometry experiments of chlorine dioxide are presented in Chapter 3. Upon excitation to the A {sup 2}A{sub 2} state near 3.2 eV, the molecule dissociates through an indirect two-step mechanism. The direct dissociation channel has been predicted to be open, but is not observed. A quantum beat is observed in the OClO{sup +} species, which is described as a vibrational coherence of the optically prepared A {sup 2}A{sub 2} state. Chapter 4 presents the results of the time-resolved photoelectron experiments of chlorine dioxide. At short delay time, the quantum beat of the OClO{sup +} species is observed in the X {sup 1}A{sub 1} state of the ion. At infinite delay, the signal

Time resolved techniques: An overview

International Nuclear Information System (INIS)

Larson, B.C.; Tischler, J.Z.

1990-06-01

Synchrotron sources provide exceptional opportunities for carrying out time-resolved x-ray diffraction investigations. The high intensity, high angular resolution, and continuously tunable energy spectrum of synchrotron x-ray beams lend themselves directly to carrying out sophisticated time-resolved x-ray scattering measurements on a wide range of materials and phenomena. When these attributes are coupled with the pulsed time-structure of synchrotron sources, entirely new time-resolved scattering possibilities are opened. Synchrotron beams typically consist of sub-nanosecond pulses of x-rays separated in time by a few tens of nanoseconds to a few hundred nanoseconds so that these beams appear as continuous x-ray sources for investigations of phenomena on time scales ranging from hours down to microseconds. Studies requiring time-resolution ranging from microseconds to fractions of a nanosecond can be carried out in a triggering mode by stimulating the phenomena under investigation in coincidence with the x-ray pulses. Time resolution on the picosecond scale can, in principle, be achieved through the use of streak camera techniques in which the time structure of the individual x-ray pulses are viewed as quasi-continuous sources with ∼100--200 picoseconds duration. Techniques for carrying out time-resolved scattering measurements on time scales varying from picoseconds to kiloseconds at present and proposed synchrotron sources are discussed and examples of time-resolved studies are cited. 17 refs., 8 figs

Direct Imaging of Transient Fano Resonances in N_{2} Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy.

Science.gov (United States)

Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J J; Kornilov, Oleg

2016-04-22

Autoionizing Rydberg states of molecular N_{2} are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14±1  fs, while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance.

Multi-Channel Amplifier-Discriminator for Highly Time-Resolved Detection

CERN Document Server

Despeisse, M; Lapington, J; Jarron, P

2011-01-01

A low-power multi-channel amplifier-discriminator was developed for application in highly time-resolved detection systems. The proposed circuit architecture, so-called Nino, is based on a time-over-threshold approach and shows a high potential for time-resolved readout of solid-state photo-detectors and of detectors based on vacuum technologies. The Irpics circuit was designed in a 250 nm CMOS technology, implementing 32 channels of a Nino version optimized to achieve high-time resolution on the output low-voltage differential signals (LVDS) while keeping a low power consumption of 10 mW per channel. Electrical characterizations of the circuit demonstrate a very low intrinsic time jitter on the output pulse leading edge, measured below 10 ps rms for each channel for high input signal charges (100 fC) and below 25 ps rms for low input signal charges (20-100 fC). The read-out architecture moreover permits to retrieve the input signal charge from the timing measurements, while a calibration procedure was develop...

Life-time resolved emission spectra in CdCl2 crystals

International Nuclear Information System (INIS)

Kawabata, S.; Nakagawa, H.; Kitaura, M.

2005-01-01

The emission spectrum of CdCl 2 is composed of ultraviolet (UV) and yellow (Y) bands peaking at 3.70 and 2.30 eV, respectively. In order to determine the initial states of the Y-luminescence, decay curves of the Y-emission were measured at 8K by varying emission energy in the range from 1.64 eV to 3.13 eV. The observed decay curves are composed of two or three exponential components. The values of lifetime for them were 900, 460 and 60 μs. The emission spectrum for each decay component, i.e., life-time resolved emission spectrum, was analyzed by the observed decay curves. The emission spectrum for the component of 460 μs lifetime exhibits a dominant band at 2.30 eV and a satellite band at 3.03 eV. The emission spectrum for the component of 60 μs lifetime is reproduced by the three Gaussian bands peaking at 2.21, 2.65 and 2.87 eV. For the component of 900 μs lifetime, only a single band appears at 1.73 eV. The origin of the emission bands in life-time resolved emission spectra is briefly discussed, and the initial states of Y-luminescence are explained by the excited states of a [Cd 2+ Cl - 6 ] 4- complex molecular ion. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Determining grain resolved stresses in polycrystalline materials using three-dimensional X-ray diffraction

DEFF Research Database (Denmark)

Oddershede, Jette; Schmidt, Søren; Poulsen, Henning Friis

2010-01-01

An algorithm is presented for characterization of the grain resolved (type II) stress states in a polycrystalline sample based on monochromatic X-ray diffraction data. The algorithm is a robust 12-parameter-per-grain fit of the centre-of-mass grain positions, orientations and stress tensors...

Creating diversified response profiles from a single quenchometric sensor element by using phase-resolved luminescence.

Science.gov (United States)

Tehan, Elizabeth C; Bukowski, Rachel M; Chodavarapu, Vamsy P; Titus, Albert H; Cartwright, Alexander N; Bright, Frank V

2015-01-05

We report a new strategy for generating a continuum of response profiles from a single luminescence-based sensor element by using phase-resolved detection. This strategy yields reliable responses that depend in a predictable manner on changes in the luminescent reporter lifetime in the presence of the target analyte, the excitation modulation frequency, and the detector (lock-in amplifier) phase angle. In the traditional steady-state mode, the sensor that we evaluate exhibits a linear, positive going response to changes in the target analyte concentration. Under phase-resolved conditions the analyte-dependent response profiles: (i) can become highly non-linear; (ii) yield negative going responses; (iii) can be biphasic; and (iv) can exhibit super sensitivity (e.g., sensitivities up to 300 fold greater in comparison to steady-state conditions).

Time-resolved photoelectron spectroscopy of IR-driven electron dynamics in a charge transfer model system.

Science.gov (United States)

Falge, Mirjam; Fröbel, Friedrich Georg; Engel, Volker; Gräfe, Stefanie

2017-08-02

If the adiabatic approximation is valid, electrons smoothly adapt to molecular geometry changes. In contrast, as a characteristic of diabatic dynamics, the electron density does not follow the nuclear motion. Recently, we have shown that the asymmetry in time-resolved photoelectron spectra serves as a tool to distinguish between these dynamics [Falge et al., J. Phys. Chem. Lett., 2012, 3, 2617]. Here, we investigate the influence of an additional, moderately intense infrared (IR) laser field, as often applied in attosecond time-resolved experiments, on such asymmetries. This is done using a simple model for coupled electronic-nuclear motion. We calculate time-resolved photoelectron spectra and their asymmetries and demonstrate that the spectra directly map the bound electron-nuclear dynamics. From the asymmetries, we can trace the IR field-induced population transfer and both the field-driven and intrinsic (non-)adiabatic dynamics. This holds true when considering superposition states accompanied by electronic coherences. The latter are observable in the asymmetries for sufficiently short XUV pulses to coherently probe the coupled states. It is thus documented that the asymmetry is a measure for phases in bound electron wave packets and non-adiabatic dynamics.

A dual cryogenic ion trap spectrometer for the formation and characterization of solvated ionic clusters

Energy Technology Data Exchange (ETDEWEB)

Marsh, Brett M.; Voss, Jonathan M.; Garand, Etienne, E-mail: egarand@chem.wisc.edu [Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706 (United States)

2015-11-28

A new experimental approach is presented in which two separate cryogenic ion traps are used to reproducibly form weakly bound solvent clusters around electrosprayed ions and messenger-tag them for single-photon infrared photodissociation spectroscopy. This approach thus enables the vibrational characterization of ionic clusters comprised of a solvent network around large and non-volatile ions. We demonstrate the capabilities of the instrument by clustering water, methanol, and acetone around a protonated glycylglycine peptide. For water, cluster sizes with greater than twenty solvent molecules around a single ion are readily formed. We further demonstrate that similar water clusters can be formed around ions having a shielded charge center or those that do not readily form hydrogen bonds. Finally, infrared photodissociation spectra of D{sub 2}-tagged GlyGlyH{sup +} ⋅ (H{sub 2}O){sub 1−4} are presented. They display well-resolved spectral features and comparisons with calculations reveal detailed information on the solvation structures of this prototypical peptide.

Mixed quantum/classical investigation of the photodissociation of NH3(A) and a practical method for maintaining zero-point energy in classical trajectories.

Science.gov (United States)

Bonhommeau, David; Truhlar, Donald G

2008-07-07

The photodissociation dynamics of ammonia upon excitation of the out-of-plane bending mode (mode nu(2) with n(2)=0,[ellipsis (horizontal)],6 quanta of vibration) in the A electronic state is investigated by means of several mixed quantum/classical methods, and the calculated final-state properties are compared to experiments. Five mixed quantum/classical methods are tested: one mean-field approach (the coherent switching with decay of mixing method), two surface-hopping methods [the fewest switches with time uncertainty (FSTU) and FSTU with stochastic decay (FSTU/SD) methods], and two surface-hopping methods with zero-point energy (ZPE) maintenance [the FSTUSD+trajectory projection onto ZPE orbit (TRAPZ) and FSTUSD+minimal TRAPZ (mTRAPZ) methods]. We found a qualitative difference between final NH(2) internal energy distributions obtained for n(2)=0 and n(2)>1, as observed in experiments. Distributions obtained for n(2)=1 present an intermediate behavior between distributions obtained for smaller and larger n(2) values. The dynamics is found to be highly electronically nonadiabatic with all these methods. NH(2) internal energy distributions may have a negative energy tail when the ZPE is not maintained throughout the dynamics. The original TRAPZ method was designed to maintain ZPE in classical trajectories, but we find that it leads to unphysically high internal vibrational energies. The mTRAPZ method, which is new in this work and provides a general method for maintaining ZPE in either single-surface or multisurface trajectories, does not lead to unphysical results and is much less time consuming. The effect of maintaining ZPE in mixed quantum/classical dynamics is discussed in terms of agreement with experimental findings. The dynamics for n(2)=0 and n(2)=6 are also analyzed to reveal details not available from experiment, in particular, the time required for quenching of electronic excitation and the adiabatic energy gap and geometry at the time of quenching.

Mixed quantum/classical investigation of the photodissociation of NH3(Ã) and a practical method for maintaining zero-point energy in classical trajectories

Science.gov (United States)

Bonhommeau, David; Truhlar, Donald G.

2008-07-01

The photodissociation dynamics of ammonia upon excitation of the out-of-plane bending mode (mode ν2 with n2=0,…,6 quanta of vibration) in the à electronic state is investigated by means of several mixed quantum/classical methods, and the calculated final-state properties are compared to experiments. Five mixed quantum/classical methods are tested: one mean-field approach (the coherent switching with decay of mixing method), two surface-hopping methods [the fewest switches with time uncertainty (FSTU) and FSTU with stochastic decay (FSTU/SD) methods], and two surface-hopping methods with zero-point energy (ZPE) maintenance [the FSTU /SD+trajectory projection onto ZPE orbit (TRAPZ) and FSTU /SD+minimal TRAPZ (mTRAPZ) methods]. We found a qualitative difference between final NH2 internal energy distributions obtained for n2=0 and n2>1, as observed in experiments. Distributions obtained for n2=1 present an intermediate behavior between distributions obtained for smaller and larger n2 values. The dynamics is found to be highly electronically nonadiabatic with all these methods. NH2 internal energy distributions may have a negative energy tail when the ZPE is not maintained throughout the dynamics. The original TRAPZ method was designed to maintain ZPE in classical trajectories, but we find that it leads to unphysically high internal vibrational energies. The mTRAPZ method, which is new in this work and provides a general method for maintaining ZPE in either single-surface or multisurface trajectories, does not lead to unphysical results and is much less time consuming. The effect of maintaining ZPE in mixed quantum/classical dynamics is discussed in terms of agreement with experimental findings. The dynamics for n2=0 and n2=6 are also analyzed to reveal details not available from experiment, in particular, the time required for quenching of electronic excitation and the adiabatic energy gap and geometry at the time of quenching.

Time-resolved and steady-state studies of biologically and chemically relevant systems using laser, absorption, and fluorescence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Barnes, Charles Ashley [Iowa State Univ., Ames, IA (United States)

2014-12-20

In Chapter 2 several experimental and data analysis methods used in this thesis are described. In Chapter 3 steady-state fluorescence spectroscopy was used to determine the concentration of the efflux pump inhibitors (EPIs), pheophorbide a and pyropheophorbide a, in the feces of animals and it was found that their levels far exceed those reported to be inhibitory to efflux pumps. In Chapter 4 the solvation dynamics of 6-Propionyl-2-(N,Ndimethyl) aminonaphthalene (PRODAN) was studied in reverse micelles. The two fluorescent states of PRODAN solvate on different time scales and as such care must be exercised in solvation dynamic studies involving it and its analogs. In Chapter 5 we studied the experimental and theoretical solvation dynamics of coumarin 153 (C153) in wild-type (WT) and modified myoglobins. Based on the nuclear magnetic resonance (NMR) spectroscopy and time-resolved fluorescence studies, we have concluded that it is important to thoroughly characterize the structure of a protein and probe system before comparing the theoretical and experimental results. In Chapter 6 the photophysical and spectral properties of a derivative of the medically relevant compound curcumin called cyclocurcumin was studied. Based on NMR, fluorescence, and absorption studies, the ground- and excited-states of cyclocurcumin are complicated by the existence of multiple structural isomers. In Chapter 7 the hydrolysis of cellulose by a pure form of cellulase in an ionic liquid, HEMA, and its aqueous mixtures at various temperatures were studied with the goal of increasing the cellulose to glucose conversion for biofuel production. It was found that HEMA imparts an additional stability to cellulase and can allow for faster conversion of cellulose to glucose using a pre-treatment step in comparison to only buffer.

Atomic and Molecular Data for State-Resolved Modelling of Hydrogen and Helium and Their Isotopes in Fusion Plasma. Summary Report of the First Research Coordination Meeting

International Nuclear Information System (INIS)

Braams, B. J.

2013-12-01

The First Research Coordination Meeting of the IAEA Coordinated Research Project (CRP) on 'Atomic and Molecular Data for State-Resolved Modelling of Hydrogen and Helium and Their Isotopes in Fusion Plasma' was held 10-12 August 2011 at IAEA Headquarters in Vienna. Participants reviewed the status of the database on molecular processes of H and He, identified data needs and made plans for development of new data in connection with the CRP. The proceedings of the meeting are summarized here. Participants' summaries and work plans are also provided. (author)

Time-resolved absorption measurements on OMEGA

International Nuclear Information System (INIS)

Jaanimagi, P.A.; DaSilva, L.; Delettrez, J.; Gregory, G.G.; Richardson, M.C.

1986-01-01

Time-resolved measurements of the incident laser light that is scattered and/or refracted from targets irradiated by the 24 uv-beam OMEGA laser at LLE, have provided some interesting features related to time-resolved absorption. The decrease in laser absorption characteristic of irradiating a target that implodes during the laser pulse has been observed. The increase in absorption expected as the critical density surface moves from a low to a high Z material in the target has also been noted. The detailed interpretation of these results is made through comparisons with simulation using the code LILAC, as well as with streak data from time-resolved x-ray imaging and spectroscopy. In addition, time and space-resolved imaging of the scattered light yields information on laser irradiation uniformity conditions on the target. The report consists of viewgraphs

Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC+)

International Nuclear Information System (INIS)

Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Ng, C. Y.; Yin, Qing-Zhu

2014-01-01

Titanium carbide and its cation (TiC/TiC + ) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16 446 and 16 930 cm −1 . Based on rotational analyses, these bands are assigned as the respective TiC( 3 Π 1 ) ← TiC(X 3 Σ + ) and TiC( 3 Σ + ) ← TiC(X 3 Σ + ) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ 2 8σ 1 9σ 1 3π 4 (X 3 Σ + ). The rotational constant and the corresponding bond distance of TiC(X 3 Σ + ; v″ = 0) are determined to be B 0 ″ = 0.6112(10) cm −1 and r 0 ″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC + (X; v + = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC + ground state are …7σ 2 8σ 1 3π 4 (X 2 Σ + ) with the v + = 0 → 1 vibrational spacing of 870.0(8) cm −1 and the rotational constants of B e + = 0.6322(28) cm −1 , and α e + = 0.0085(28) cm −1 . The latter rotational constants yield the equilibrium bond distance of r e + = 1.667(4) Å for TiC + (X 2 Σ + ). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm −1 [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D 0 ) of TiC + (X 2 Σ + ) and that of TiC(X 3 Σ + ) to be D 0 (Ti + −C) − D 0 (Ti−C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC + (X 2 Σ + ; v + = 0 and 1, N + ) ← TiC( 3 Π 1 ; v′, J′), reveals a strong decreasing trend for the photoionization cross

Time-Resolved Magnetic Field Effects Distinguish Loose Ion Pairs from Exciplexes

Science.gov (United States)

2013-01-01

We describe the experimental investigation of time-resolved magnetic field effects in exciplex-forming organic donor–acceptor systems. In these systems, the photoexcited acceptor state is predominantly deactivated by bimolecular electron transfer reactions (yielding radical ion pairs) or by direct exciplex formation. The delayed fluorescence emitted by the exciplex is magnetosensitive if the reaction pathway involves loose radical ion pair states. This magnetic field effect results from the coherent interconversion between the electronic singlet and triplet radical ion pair states as described by the radical pair mechanism. By monitoring the changes in the exciplex luminescence intensity when applying external magnetic fields, details of the reaction mechanism can be elucidated. In this work we present results obtained with the fluorophore-quencher pair 9,10-dimethylanthracene/N,N-dimethylaniline (DMA) in solvents of systematically varied permittivity. A simple theoretical model is introduced that allows discriminating the initial state of quenching, viz., the loose ion pair and the exciplex, based on the time-resolved magnetic field effect. The approach is validated by applying it to the isotopologous fluorophore-quencher pairs pyrene/DMA and pyrene-d10/DMA. We detect that both the exciplex and the radical ion pair are formed during the initial quenching stage. Upon increasing the solvent polarity, the relative importance of the distant electron transfer quenching increases. However, even in comparably polar media, the exciplex pathway remains remarkably significant. We discuss our results in relation to recent findings on the involvement of exciplexes in photoinduced electron transfer reactions. PMID:24041160

Healthcare Teams Neurodynamically Reorganize When Resolving Uncertainty

Directory of Open Access Journals (Sweden)

Ronald Stevens

2016-11-01

Full Text Available Research on the microscale neural dynamics of social interactions has yet to be translated into improvements in the assembly, training and evaluation of teams. This is partially due to the scale of neural involvements in team activities, spanning the millisecond oscillations in individual brains to the minutes/hours performance behaviors of the team. We have used intermediate neurodynamic representations to show that healthcare teams enter persistent (50–100 s neurodynamic states when they encounter and resolve uncertainty while managing simulated patients. Each of the second symbols was developed situating the electroencephalogram (EEG power of each team member in the contexts of those of other team members and the task. These representations were acquired from EEG headsets with 19 recording electrodes for each of the 1–40 Hz frequencies. Estimates of the information in each symbol stream were calculated from a 60 s moving window of Shannon entropy that was updated each second, providing a quantitative neurodynamic history of the team’s performance. Neurodynamic organizations fluctuated with the task demands with increased organization (i.e., lower entropy occurring when the team needed to resolve uncertainty. These results show that intermediate neurodynamic representations can provide a quantitative bridge between the micro and macro scales of teamwork.

Imposing resolved turbulence in CFD simulations

DEFF Research Database (Denmark)

Gilling, L.; Sørensen, Niels N.

2011-01-01

In large‐eddy simulations, the inflow velocity field should contain resolved turbulence. This paper describes and analyzes two methods for imposing resolved turbulence in the interior of the domain in Computational Fluid Dynamics simulations. The intended application of the methods is to impose...

Rotationally resolved state-to-state photoionization and photoelectron study of titanium carbide and its cation (TiC/TiC⁺).

Science.gov (United States)

Luo, Zhihong; Huang, Huang; Chang, Yih-Chung; Zhang, Zheng; Yin, Qing-Zhu; Ng, C Y

2014-10-14

Titanium carbide and its cation (TiC/TiC(+)) have been investigated by the two-color visible (VIS)-ultraviolet (UV) resonance-enhanced photoionization and pulsed field ionization-photoelectron (PFI-PE) methods. Two visible excitation bands for neutral TiC are observed at 16,446 and 16,930 cm(-1). Based on rotational analyses, these bands are assigned as the respective TiC((3)Π1) ← TiC(X(3)Σ(+)) and TiC((3)Σ(+)) ← TiC(X(3)Σ(+)) transition bands. This assignment supports that the electronic configuration and term symmetry for the neutral TiC ground state are …7σ(2)8σ(1)9σ(1)3π(4) (X(3)Σ(+)). The rotational constant and the corresponding bond distance of TiC(X(3)Σ(+); v″ = 0) are determined to be B0″ = 0.6112(10) cm(-1) and r0″ = 1.695(2) Å, respectively. The rotational analyses of the VIS-UV-PFI-PE spectra for the TiC(+)(X; v(+) = 0 and 1) vibrational bands show that the electronic configuration and term symmetry for the ionic TiC(+) ground state are …7σ(2)8σ(1)3π(4) (X(2)Σ(+)) with the v(+) = 0 → 1 vibrational spacing of 870.0(8) cm(-1) and the rotational constants of B(e)(+) = 0.6322(28) cm(-1), and α(e)(+) = 0.0085(28) cm(-1). The latter rotational constants yield the equilibrium bond distance of r(e)(+) = 1.667(4) Å for TiC(+)(X(2)Σ(+)). The cleanly rotationally resolved VIS-UV-PFI-PE spectra have also provided a highly precise value of 53 200.2(8) cm(-1) [6.5960(1) eV] for the adiabatic ionization energy (IE) of TiC. This IE(TiC) value along with the known IE(Ti) has made possible the determination of the difference between the 0 K bond dissociation energy (D0) of TiC(+)(X(2)Σ(+)) and that of TiC(X(3)Σ(+)) to be D0(Ti(+)-C) - D0(Ti-C) = 0.2322(2) eV. Similar to previous experimental observations, the present state-to-state PFI-PE study of the photoionization transitions, TiC(+)(X(2)Σ(+); v(+) = 0 and 1, N(+)) ← TiC((3)Π1; v', J'), reveals a strong decreasing trend for the photoionization cross section as |ΔN(+)| = |N

Spatially resolved density and ionization measurements of shocked foams using x-ray fluorescence

Energy Technology Data Exchange (ETDEWEB)

MacDonald, M. J.; Keiter, P. A.; Montgomery, D. S.; Scott, H. A.; Biener, M. M.; Fein, J. R.; Fournier, K. B.; Gamboa, E. J.; Kemp, G. E.; Klein, S. R.; Kuranz, C. C.; LeFevre, H. J.; Manuel, M. J. -E.; Wan, W. C.; Drake, R. P.

2016-09-28

We present experiments at the Trident laser facility demonstrating the use of x-ray fluorescence (XRF) to simultaneously measure density, ionization state populations, and electron temperature in shocked foams. An imaging x-ray spectrometer obtained spatially resolved measurements of Ti K-α emission. Density profiles were measured from K-α intensity. Ti ionization state distributions and electron temperatures were inferred by fitting K-α spectra to spectra from CRETIN simulations. This work shows that XRF provides a powerful tool to complement other diagnostics to make equation of state measurements of shocked materials containing a suitable tracer element.

State-resolved Thermal/Hyperthermal Dynamics of Atmospheric Species

Science.gov (United States)

2015-06-23

M. Zolot, W. W. Harper , B. G. Perkins, P. J. Dagdigian, and D. J. Nesbitt, J. Chem. Phys. 125 (2) (2006). 4 B. G. Perkins and D. J. Nesbitt, Proc...Quantum Dots to Biomolecules,” Department of Chemistry and Biochemistry , Florida State University, Tallahassee, FL, March 18, 2011. DISTRIBUTION A

Knowledge Extraction from Atomically Resolved Images.

Science.gov (United States)

Vlcek, Lukas; Maksov, Artem; Pan, Minghu; Vasudevan, Rama K; Kalinin, Sergei V

2017-10-24

Tremendous strides in experimental capabilities of scanning transmission electron microscopy and scanning tunneling microscopy (STM) over the past 30 years made atomically resolved imaging routine. However, consistent integration and use of atomically resolved data with generative models is unavailable, so information on local thermodynamics and other microscopic driving forces encoded in the observed atomic configurations remains hidden. Here, we present a framework based on statistical distance minimization to consistently utilize the information available from atomic configurations obtained from an atomically resolved image and extract meaningful physical interaction parameters. We illustrate the applicability of the framework on an STM image of a FeSe x Te 1-x superconductor, with the segregation of the chalcogen atoms investigated using a nonideal interacting solid solution model. This universal method makes full use of the microscopic degrees of freedom sampled in an atomically resolved image and can be extended via Bayesian inference toward unbiased model selection with uncertainty quantification.

Non-destructive state detection for quantum logic spectroscopy of molecular ions.

Science.gov (United States)

Wolf, Fabian; Wan, Yong; Heip, Jan C; Gebert, Florian; Shi, Chunyan; Schmidt, Piet O

2016-02-25

Precision laser spectroscopy of cold and trapped molecular ions is a powerful tool in fundamental physics--used, for example, in determining fundamental constants, testing for their possible variation in the laboratory, and searching for a possible electric dipole moment of the electron. However, the absence of cycling transitions in molecules poses a challenge for direct laser cooling of the ions, and for controlling and detecting their quantum states. Previously used state-detection techniques based on photodissociation or chemical reactions are destructive and therefore inefficient, restricting the achievable resolution in laser spectroscopy. Here, we experimentally demonstrate non-destructive detection of the quantum state of a single trapped molecular ion through its strong Coulomb coupling to a well controlled, co-trapped atomic ion. An algorithm based on a state-dependent optical dipole force changes the internal state of the atom according to the internal state of the molecule. We show that individual quantum states in the molecular ion can be distinguished by the strength of their coupling to the optical dipole force. We also observe quantum jumps (induced by black-body radiation) between rotational states of a single molecular ion. Using the detuning dependence of the state-detection signal, we implement a variant of quantum logic spectroscopy of a molecular resonance. Our state-detection technique is relevant to a wide range of molecular ions, and could be applied to state-controlled quantum chemistry and to spectroscopic investigations of molecules that serve as probes for interstellar clouds.

Molecular beam studies of stratospheric photochemistry

Science.gov (United States)

Moore, Teresa Anne

1998-12-01

Photochemistry of chlorine oxide containing species plays a major role in stratospheric ozone depletion. This thesis discusses two photodissociation studies of the key molecules ClONO2 and ClOOCl which were previously thought to only produce Cl-atom (ozone depleting) products at wavelengths relevant to the stratosphere. The development of a molecular beam source of ClOOCl and the photodissociation dynamics of the model system Cl2O are also discussed. In the first chapter, the photochemistry of ClONO2 is examined at 308 nm using the technique of photofragment translational spectroscopy. Two primary decomposition pathways, leading to Cl + NO3 and ClO + NO2, were observed, with a lower limit of 0.33 for the relative yield of ClO. The angular distributions for both channels were anisotropic, indicating that the dissociation occurs within a rotational period. Chapter two revisits the photodissociation dynamics of Cl2O at 248 and 308 nm, on which we had previously reported preliminary findings. At 248 nm, three distinct dissociation pathways leading to Cl + ClO products were resolved. At 308 nm, the angular distribution was slightly more isotropic that previously reported, leaving open the possibility that Cl2O excited at 308 nm lives longer than a rotational period. Chapter three describes the development and optimization of a molecular beam source of ClOOCl. We utilized pulsed laser photolysis of ClA2O to generate ClO radicals, and cooled the cell to promote three body recombination to form ClOOCl. The principal components in the beam were Cl2, Cl2O, and ClOOCl. In the fourth chapter, the photodissociation dynamics of ClOOCl are investigated at 248 and 308 nm. We observed multiple dissociation pathways which produced ClO + ClO and 2Cl + O2 products. The relative Cl:ClO product yields are 1.0:0.13 and 1.0:0.20 for ClOOCl photolysis at 248 and 308 nm, respectively. The upper limit for the relative yield of the ClO + ClO channel was 0.19 at 248 nm and 0.31 at 308 nm

Mixed quantum/classical investigation of the photodissociation of NH3(A-tilde) and a practical method for maintaining zero-point energy in classical trajectories

International Nuclear Information System (INIS)

Bonhommeau, David; Truhlar, Donald G.

2008-01-01

The photodissociation dynamics of ammonia upon excitation of the out-of-plane bending mode (mode ν 2 with n 2 =0,...,6 quanta of vibration) in the A-tilde electronic state is investigated by means of several mixed quantum/classical methods, and the calculated final-state properties are compared to experiments. Five mixed quantum/classical methods are tested: one mean-field approach (the coherent switching with decay of mixing method), two surface-hopping methods [the fewest switches with time uncertainty (FSTU) and FSTU with stochastic decay (FSTU/SD) methods], and two surface-hopping methods with zero-point energy (ZPE) maintenance [the FSTU/SD+trajectory projection onto ZPE orbit (TRAPZ) and FSTU/SD+minimal TRAPZ (mTRAPZ) methods]. We found a qualitative difference between final NH 2 internal energy distributions obtained for n 2 =0 and n 2 >1, as observed in experiments. Distributions obtained for n 2 =1 present an intermediate behavior between distributions obtained for smaller and larger n 2 values. The dynamics is found to be highly electronically nonadiabatic with all these methods. NH 2 internal energy distributions may have a negative energy tail when the ZPE is not maintained throughout the dynamics. The original TRAPZ method was designed to maintain ZPE in classical trajectories, but we find that it leads to unphysically high internal vibrational energies. The mTRAPZ method, which is new in this work and provides a general method for maintaining ZPE in either single-surface or multisurface trajectories, does not lead to unphysical results and is much less time consuming. The effect of maintaining ZPE in mixed quantum/classical dynamics is discussed in terms of agreement with experimental findings. The dynamics for n 2 =0 and n 2 =6 are also analyzed to reveal details not available from experiment, in particular, the time required for quenching of electronic excitation and the adiabatic energy gap and geometry at the time of quenching

Laser wakefield generated X-ray probe for femtosecond time-resolved measurements of ionization states of warm dense aluminum

Energy Technology Data Exchange (ETDEWEB)

Mo, M. Z.; Chen, Z.; Tsui, Y. Y.; Fedosejevs, R. [Department of Electrical and Computer Engineering, University of Alberta, Edmonton, Alberta T6G 2V4 (Canada); Fourmaux, S.; Saraf, A.; Otani, K.; Kieffer, J. C. [INRS-EMT, Université du Québec, 1650 Lionel Boulet, Varennes, Québec J3X 1S2 (Canada); Ng, A. [Department of Physics and Astronomy, University of British Columbia, British Columbia V6T 1Z1 (Canada)

2013-12-15

We have developed a laser wakefield generated X-ray probe to directly measure the temporal evolution of the ionization states in warm dense aluminum by means of absorption spectroscopy. As a promising alternative to the free electron excited X-ray sources, Betatron X-ray radiation, with femtosecond pulse duration, provides a new technique to diagnose femtosecond to picosecond transitions in the atomic structure. The X-ray probe system consists of an adjustable Kirkpatrick-Baez (KB) microscope for focusing the Betatron emission to a small probe spot on the sample being measured, and a flat Potassium Acid Phthalate Bragg crystal spectrometer to measure the transmitted X-ray spectrum in the region of the aluminum K-edge absorption lines. An X-ray focal spot size of around 50 μm was achieved after reflection from the platinum-coated 10-cm-long KB microscope mirrors. Shot to shot positioning stability of the Betatron radiation was measured resulting in an rms shot to shot variation in spatial pointing on the sample of 16 μm. The entire probe setup had a spectral resolution of ∼1.5 eV, a detection bandwidth of ∼24 eV, and an overall photon throughput efficiency of the order of 10{sup −5}. Approximately 10 photons were detected by the X-ray CCD per laser shot within the spectrally resolved detection band. Thus, it is expected that hundreds of shots will be required per absorption spectrum to clearly observe the K-shell absorption features expected from the ionization states of the warm dense aluminum.

Surface investigations using monolayer-resolvable high-resolution Rutherford backscattering spectroscopy

International Nuclear Information System (INIS)

Kimura, Kenji; Ohtsuka, Hisashi; Ohshima, Kazuomi; Mannami, Michi-hiko

1994-01-01

Energy spectra of scattered 0.5 MeV He ions from a clean (001) surface of SnTe are measured with a 90 sector magnetic spectrometer (ΔE/E ∼ 0.1%). The ions scattered from successive atomic layers can be resolved in the energy spectra. Inelastic energy losses and charge state distributions of 0.5 MeV He ions scattered from the topmost atomic layer of the SnTe(001) are measured. A position-dependent stopping power at the surface is proposed from the observed energy losses. The observed charge state distribution shows the importance of the charge-exchange processes with valence electrons in the tail of the electron distribution at the surface. (orig.)

Femtosecond time-resolved two-photon photoemission study of organic semiconductor copper phthalocyanine film

International Nuclear Information System (INIS)

Tanaka, A.; Tohoku University; University of Rochester, NY; Yan, L.; Watkins, N.J.; Gao, Y.

2004-01-01

Full text: Organic semiconductors are recently attracting much interest from the viewpoints of both device and fundamental physics. These organic semiconductors are considered to be important constituents of the future devices, such as organic light-emitting diode, organic field effect transistor, and organic solid-state injection laser. In order to elucidate their detailed physical properties and to develop the future devices, it is indispensable to understand their excited-state dynamics as well as their electronic structures. The femtosecond time-resolved two-photon photoemission (TR-2PPE) spectroscopy is attracting much interest because of its capability to observe the energy-resolved excited electron dynamics. In this work, we have carried out a TR-2PPE study of the organic semiconductor copper phthalocyanine (CuPc) film. Furthermore, we have investigated the detailed electronic structure of CuPc film using the photoemission (PES) and inverse photoemission (IPES) spectroscopies. From the simultaneous PES and IPES measurements for CuPc film with a thickness of 100 nm, the lowest unoccupied molecular orbital (LUMO), highest occupied molecular orbital, and ionization potential of CuPc film have been directly determined. The observed two-photon photoemission (2PPE) spectrum of the present CuPc film, measured with photon energy of about hv=3.3 eV, exhibits a broad feature. From the energy diagram of CuPc film determined by the PES and IPES measurements, the intermediate state observed in the present 2PPE spectrum of CuPc film corresponds to the energy region between about 0.4 and 1.7 eV above the LUMO energy. From the time-resolved pump-probe measurements, it is found that the relaxation lifetimes of excited states in the present CuPc films are very short (all below 50 fs) and monotonously become faster with increasing excitation energy. We attribute this extremely fast relaxation process of photoexcitation to a rapid internal conversion process. From these results

Time-resolved diode laser infrared absorption spectroscopy of the nascent HCl in the infrared laser chemistry of 1,2-dichloro-1,1-difluoroethane

Science.gov (United States)

Dietrich, Peter; Quack, Martin; Seyfang, George

1990-04-01

The IR multiphoton excitation and the frequency, fluence and intensity dependence of the IR-laser chemical yields of CF 2ClCH 2Cl have been studied in the fluence range of 1 to 10 J cm -2 yielding a steady-state constant k(st)/ I=0.74×10 6 s -1 MW -1 cm 2 which is approximately independent of intensity. Time-resolved IR absorption spectroscopy with diode laser sources has been used to observe the nascent HCl during the first few 100 ns indicating a population inversion between the levels ν=1, J=4 and ν=2, J=5. At low reactant pressures ( p⩽10 Pa) the time-resolved measurement gives a steady-state rate constant consistent with the theoretical result adjusted to the static yield measurements. The capability of state-selective and time-resolved IR spectroscopy is thus demonstrated, giving real-time determinations of rate constants.

Laser isotope and isomer separations: History and trends

International Nuclear Information System (INIS)

Letok'ov, V.S.

1990-01-01

Paper will review history and principles of laser isotope and nuclear isomer separation: laser multistep photoionization of isotopic and isomeric atoms, laser IR-UV two-step photodissociation of molecules, laser IR multiphoton photodissociation of polyatomic molecules. The comparison and areas of applications of these methods will be considered. Paper will discuss a present state of art of technology of these methods in practical scale in various countries. In conclusion the trends of research in this field including applications of laser-separated isotopes and isomers will be considered

Mix and Inject: Reaction Initiation by Diffusion for Time-Resolved Macromolecular Crystallography

Directory of Open Access Journals (Sweden)

Marius Schmidt

2013-01-01

Full Text Available Time-resolved macromolecular crystallography unifies structure determination with chemical kinetics, since the structures of transient states and chemical and kinetic mechanisms can be determined simultaneously from the same data. To start a reaction in an enzyme, typically, an initially inactive substrate present in the crystal is activated. This has particular disadvantages that are circumvented when active substrate is directly provided by diffusion. However, then it is prohibitive to use macroscopic crystals because diffusion times become too long. With small micro- and nanocrystals diffusion times are adequately short for most enzymes and the reaction can be swiftly initiated. We demonstrate here that a time-resolved crystallographic experiment becomes feasible by mixing substrate with enzyme nanocrystals which are subsequently injected into the X-ray beam of a pulsed X-ray source.

Steady state and time-resolved fluorescence spectroscopy of quinine sulfate dication bound to sodium dodecylsulfate micelles: Fluorescent complex formation

Energy Technology Data Exchange (ETDEWEB)

Joshi, Sunita; Pant, Debi D., E-mail: ddpant@pilani.bits-pilani.ac.in

2014-01-15

Interaction of quinine sulfate dication (QSD) with anionic, sodium dodecylsulphate (SDS) surfactant has been studied at different premicellar, micellar and postmicellar concentrations in aqueous phase using steady state, time-resolved fluorescence and fluorescence anisotropy techniques. At premicellar concentrations of SDS, the decrease in absorbance, appearance of an extra fluorescence band at lower wavelengths and tri-exponential decay behavior of fluorescence, are attributed to complex formation between QSD molecules and surfactant monomers. At postmicellar concentrations the red shift in fluorescence spectrum, increase in quantum yield and increase in fluorescence lifetimes are attributed to incorporation of solute molecules to micelles. At lower concentrations of SDS, a large shift in fluorescence is observed on excitation at the red edge of absorption spectrum and this is explained in terms of distribution of ion pairs of different energies in the ground state and the observed fluorescence lifetime behavior corroborates with this model. The temporal fluorescence anisotropy decay of QSD in SDS micelles allowed determination of restriction on the motion of the fluorophore. All the different techniques used in this study reveal that the photophysics of QSD is very sensitive to the microenvironments of SDS micelles and QSD molecules reside at the water-micelle interface. -- Highlights: • Probe molecule is very sensitive to microenvironment of micelles. • Highly fluorescent ion-pair formation has been observed. • Modulated photophysics of probe molecule in micellar solutions has been observed. • Probe molecules strongly bind with micelles and reside at probe–micelle interface.

Grain-resolved elastic strains in deformed copper measured by three-dimensional X-ray diffraction

DEFF Research Database (Denmark)

Oddershede, Jette; Schmidt, Søren; Poulsen, Henning Friis

2011-01-01

This X-ray diffraction study reports the grain-resolved elastic strains in about 1000 randomly oriented grains embedded in a polycrystalline copper sample. Diffraction data were collected in situ in the undeformed state and at a plastic strain of 1.5% while the sample was under tensile load...

Subpicosecond oxygen trapping in the heme pocket of the oxygen sensor FixL observed by time-resolved resonance Raman spectroscopy.

Science.gov (United States)

Kruglik, Sergei G; Jasaitis, Audrius; Hola, Klara; Yamashita, Taku; Liebl, Ursula; Martin, Jean-Louis; Vos, Marten H

2007-05-01

Dissociation of oxygen from the heme domain of the bacterial oxygen sensor protein FixL constitutes the first step in hypoxia-induced signaling. In the present study, the photodissociation of the heme-O2 bond was used to synchronize this event, and time-resolved resonance Raman (TR(3)) spectroscopy with subpicosecond time resolution was implemented to characterize the heme configuration of the primary photoproduct. TR(3) measurements on heme-oxycomplexes are highly challenging and have not yet been reported. Whereas in all other known six-coordinated heme protein complexes with diatomic ligands, including the oxymyoglobin reported here, heme iron out-of-plane motion (doming) occurs faster than 1 ps after iron-ligand bond breaking; surprisingly, no sizeable doming is observed in the oxycomplex of the Bradyrhizobium japonicum FixL sensor domain (FixLH). This assessment is deduced from the absence of the iron-histidine band around 217 cm(-1) as early as 0.5 ps. We suggest that efficient ultrafast oxygen rebinding to the heme occurs on the femtosecond time scale, thus hindering heme doming. Comparing WT oxy-FixLH, mutant proteins FixLH-R220H and FixLH-R220Q, the respective carbonmonoxy-complexes, and oxymyoglobin, we show that a hydrogen bond of the terminal oxygen atom with the residue in position 220 is responsible for the observed behavior; in WT FixL this residue is arginine, crucially implicated in signal transmission. We propose that the rigid O2 configuration imposed by this residue, in combination with the hydrophobic and constrained properties of the distal cavity, keep dissociated oxygen in place. These results uncover the origin of the "oxygen cage" properties of this oxygen sensor protein.

Time-resolved ESR spectroscopy

International Nuclear Information System (INIS)

Beckert, D.

1986-06-01

The time-resolved ESR spectroscopy is one of the modern methods in radiospectroscopy and plays an important role in solving various problems in chemistry and biology. Proceeding from the basic ideas of time-resolved ESR spectroscopy the experimental equipment is described generally including the equipment developed at the Central Institute of Isotope and Radiation Research. The experimental methods applied to the investigation of effects of chemically induced magnetic polarization of electrons and to kinetic studies of free radicals in polymer systems are presented. The theory of radical pair mechanism is discussed and theoretical expressions are summarized in a computer code to compute the theoretical polarization for each pair of the radicals

Application of spectroscopy and super-resolution microscopy: Excited state

Energy Technology Data Exchange (ETDEWEB)

Bhattacharjee, Ujjal [Iowa State Univ., Ames, IA (United States)

2016-02-19

Photophysics of inorganic materials and organic molecules in complex systems have been extensively studied with absorption and emission spectroscopy.1-4 Steady-state and time-resolved fluorescence studies are commonly carried out to characterize excited-state properties of fluorophores. Although steady-state fluorescence measurements are widely used for analytical applications, time-resolved fluorescence measurements provide more detailed information about excited-state properties and the environment in the vicinity of the fluorophore. Many photophysical processes, such as photoinduced electron transfer (PET), rotational reorientation, solvent relaxation, and energy transfer, occur on a nanosecond (10^-9 s) timescale, thus affecting the lifetime of the fluorophores. Moreover, time-resolved microscopy methods, such as lifetimeimaging, combine the benefits of the microscopic measurement and information-rich, timeresolved data. Thus, time-resolved fluorescence spectroscopy combined with microscopy can be used to quantify these processes and to obtain a deeper understanding of the chemical surroundings of the fluorophore in a small area under investigation. This thesis discusses various photophysical and super-resolution microscopic studies of organic and inorganic materials, which have been outlined below.

Optical emission spectroscopy of metal-halide lamps: Radially resolved atomic state distribution functions of Dy and Hg

NARCIS (Netherlands)

Nimalasuriya, T.; Flikweert, A.J.; Stoffels, W.W.; Haverlag, M.; Mullen, van der J.J.A.M.; Pupat, N.B.M.

2006-01-01

Absolute line intensity measurements are performed on a metal-halide lamp. Several transitions of atomic and ionic Dy and atomic Hg are measured at different radial positions from which we obtain absolute atomic and ionic Dy intensity profiles. From these profiles we construct the radially resolved

Time resolved Thomson scattering diagnostic of pulsed gas metal arc welding (GMAW) process

International Nuclear Information System (INIS)

Kühn-Kauffeldt, M; Schein, J; Marquès, J L

2014-01-01

In this work a Thomson scattering diagnostic technique was applied to obtain time resolved electron temperature and density values during a gas metal arc welding (GMAW) process. The investigated GMAW process was run with aluminum wire (AlMg 4,5 Mn) with 1.2 mm diameter as a wire electrode, argon as a shielding gas and peak currents in the range of 400 A. Time resolved measurements could be achieved by triggering the laser pulse at shifted time positions with respect to the current pulse driving the process. Time evaluation of resulting electron temperatures and densities is used to investigate the state of the plasma in different phases of the current pulse and to determine the influence of the metal vapor and droplets on the plasma properties

Operation: Inherent Resolve

DEFF Research Database (Denmark)

Cramer-Larsen, Lars

2015-01-01

Kapitlet giver læseren indsigt i den internationale koalitions engagement mod IS igennem Operaton Inherent Resolve; herunder koalitionens strategi i forhold til IS strategi, ligesom det belyser kampagnens legalitet og folkeretlige grundlag, ligesom det giver et bud på overvejelser om kampagnens...

Seventh international conference on time-resolved vibrational spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Dyer, R.B.; Martinez, M.A.D.; Shreve, A.; Woodruff, W.H. [comps.

1997-04-01

The International Conference on Time-Resolved Vibrational Spectroscopy (TRVS) is widely recognized as the major international forum for the discussion of advances in this rapidly growing field. The 1995 conference was the seventh in a series that began at Lake Placid, New York, 1982. Santa Fe, New Mexico, was the site of the Seventh International Conference on Time-Resolved Vibrational Spectroscopy, held from June 11 to 16, 1995. TRVS-7 was attended by 157 participants from 16 countries and 85 institutions, and research ranging across the full breadth of the field of time-resolved vibrational spectroscopy was presented. Advances in both experimental capabilities for time-resolved vibrational measurements and in theoretical descriptions of time-resolved vibrational methods continue to occur, and several sessions of the conference were devoted to discussion of these advances and the associated new directions in TRVS. Continuing the interdisciplinary tradition of the TRVS meetings, applications of time-resolved vibrational methods to problems in physics, biology, materials science, and chemistry comprised a large portion of the papers presented at the conference.

Evidence for concerted ring opening and C-Br bond breaking in UV-excited bromocyclopropane.

Science.gov (United States)

Pandit, Shubhrangshu; Preston, Thomas J; King, Simon J; Vallance, Claire; Orr-Ewing, Andrew J

2016-06-28

Photodissociation of gaseous bromocyclopropane via its A-band continuum has been studied at excitation wavelengths ranging from 230 nm to 267 nm. Velocity-map images of ground-state bromine atoms (Br), spin-orbit excited bromine atoms (Br(∗)), and C3H5 hydrocarbon radicals reveal the kinetic energies of these various photofragments. Both Br and Br(∗) atoms are predominantly generated via repulsive excited electronic states in a prompt photodissociation process in which the hydrocarbon co-fragment is a cyclopropyl radical. However, the images obtained at the mass of the hydrocarbon radical fragment identify a channel with total kinetic energy greater than that deduced from the Br and Br(∗) images, and with a kinetic energy distribution that exceeds the energetic limit for Br + cyclopropyl radical products. The velocity-map images of these C3H5 fragments have lower angular anisotropies than measured for Br and Br(∗), indicating molecular restructuring during dissociation. The high kinetic energy C3H5 signals are assigned to allyl radicals generated by a minor photochemical pathway which involves concerted C-Br bond dissociation and cyclopropyl ring-opening following single ultraviolet (UV)-photon absorption. Slow photofragments also contribute to the velocity map images obtained at the C3H5 radical mass, but the corresponding slow Br atoms are not observed. These features in the images are attributed to C3H5 (+) from the photodissociation of the C3H5Br(+) molecular cation following two-photon ionization of the parent compound. This assignment is confirmed by 118-nm vacuum ultraviolet ionization studies that prepare the molecular cation in its ground electronic state prior to UV photodissociation.

Stimulated emission depletion microscopy resolves individual nitrogen vacancy centers in diamond nanocrystals.

OpenAIRE

Arroyo Camejo, S.; Adam, M.; Besbes, M.; Hugonin, J.; Jaques, V.; Greffet, J.; Roch, J.; Hell, S.; Treussart, F.

2013-01-01

Nitrogen-vacancy (NV) color centers in nanodiamonds are highly promising for bioimaging and sensing. However, resolving individual NV centers within nanodiamond particles and the controlled addressing and readout of their spin state has remained a major challenge. Spatially stochastic super-resolution techniques cannot provide this capability in principle, whereas coordinate-controlled super-resolution imaging methods, like stimulated emission depletion (STED) microscopy, have been predicted ...

Picosecond rotationally resolved stimulated emission pumping spectroscopy of nitric oxide

Science.gov (United States)

Tanjaroon, Chakree; Reeve, Scott W.; Ford, Alan; Murry, W. Dean; Lyon, Kevin; Yount, Bret; Britton, Dan; Burns, William A.; Allen, Susan D.; Bruce Johnson, J.

2012-01-01

Stimulated emission pumping (SEP) experiments were performed on the nitric oxide molecule in a flow cell environment using lasers with pulse widths of 17-25 ps. A lambda excitation scheme, or ''pump-dump" arrangement, was employed with the pump laser tuned to the T 00 vibronic band origin ( λ=226.35(1)nm) of the A2Σ+( v' = 0, J') ← X2Π1/2( v″ = 0, J″) and the dump laser scanned from 246-248 nm within the A2Σ+( v' = 0, J') → X2Π1/2( v″ = 2, J″) transition. The rotationally resolved SEP spectra were measured by observing the total fluorescence within the A2Σ+( v' = 0, J') → X2Π1/2( v″ = 1, J″) transition between 235 nm and 237.2 nm while scanning the dump laser wavelengths. Multiple rotational states were excited due to the broad laser bandwidth. Measurements showed that the resolved rotational structure depended on the energy and bandwidth of the applied pump and dump laser pulses. Analysis of the observed fluorescence depletion signals yielded an average percent fluorescence depletion of about 19% when λ=226.35(1)nm and λ=247.91(1)nm. This value reflects the percent transfer of the NO population from the A2Σ+( V' = 0, J') excited electronic state to the X2Π1/2( v″ = 2, J″) ground electronic state. The maximum expected depletion is 50% in the limit of dump saturation. Selective excitation of NO at the bandhead provides good spectral discrimination from the background emission and noise and unambiguously confirms the identity of the emitter.

Metal-ligand interactions

Science.gov (United States)

Ervin, Kent M.

Experimental studies of the interactions of small transition-metal cluster anions with carbonyl ligands are reviewed and compared with neutral and cationic clusters. Under thermal conditions, the reaction rates of transition-metal clusters with carbon monoxide are measured as a function of cluster size. Saturation limits for carbon monoxide addition can be related to the geometric structures of the clusters. Both energy-resolved threshold collision-induced dissociation experiments and time-resolved photodissociation experiments are used to measure metal-carbonyl binding energies. For platinum and palladium trimer anions, the carbonyl binding energies are assigned to different geometric binding sites. Platinum and palladium cluster anions catalyse the oxidation of carbon monoxide to carbon dioxide in a full catalytic cycle at thermal energies.

Watching proteins function with time-resolved x-ray crystallography

Science.gov (United States)

Šrajer, Vukica; Schmidt, Marius

2017-09-01

Macromolecular crystallography was immensely successful in the last two decades. To a large degree this success resulted from use of powerful third generation synchrotron x-ray sources. An expansive database of more than 100 000 protein structures, of which many were determined at resolution better than 2 Å, is available today. With this achievement, the spotlight in structural biology is shifting from determination of static structures to elucidating dynamic aspects of protein function. A powerful tool for addressing these aspects is time-resolved crystallography, where a genuine biological function is triggered in the crystal with a goal of capturing molecules in action and determining protein kinetics and structures of intermediates (Schmidt et al 2005a Methods Mol. Biol. 305 115-54, Schmidt 2008 Ultrashort Laser Pulses in Biology and Medicine (Berlin: Springer) pp 201-41, Neutze and Moffat 2012 Curr. Opin. Struct. Biol. 22 651-9, Šrajer 2014 The Future of Dynamic Structural Science (Berlin: Springer) pp 237-51). In this approach, short and intense x-ray pulses are used to probe intermediates in real time and at room temperature, in an ongoing reaction that is initiated synchronously and rapidly in the crystal. Time-resolved macromolecular crystallography with 100 ps time resolution at synchrotron x-ray sources is in its mature phase today, particularly for studies of reversible, light-initiated reactions. The advent of the new free electron lasers for hard x-rays (XFELs; 5-20 keV), which provide exceptionally intense, femtosecond x-ray pulses, marks a new frontier for time-resolved crystallography. The exploration of ultra-fast events becomes possible in high-resolution structural detail, on sub-picosecond time scales (Tenboer et al 2014 Science 346 1242-6, Barends et al 2015 Science 350 445-50, Pande et al 2016 Science 352 725-9). We review here state-of-the-art time-resolved crystallographic experiments both at synchrotrons and XFELs. We also outline

Spectral cumulus parameterization based on cloud-resolving model

Science.gov (United States)

Baba, Yuya

2018-02-01

We have developed a spectral cumulus parameterization using a cloud-resolving model. This includes a new parameterization of the entrainment rate which was derived from analysis of the cloud properties obtained from the cloud-resolving model simulation and was valid for both shallow and deep convection. The new scheme was examined in a single-column model experiment and compared with the existing parameterization of Gregory (2001, Q J R Meteorol Soc 127:53-72) (GR scheme). The results showed that the GR scheme simulated more shallow and diluted convection than the new scheme. To further validate the physical performance of the parameterizations, Atmospheric Model Intercomparison Project (AMIP) experiments were performed, and the results were compared with reanalysis data. The new scheme performed better than the GR scheme in terms of mean state and variability of atmospheric circulation, i.e., the new scheme improved positive bias of precipitation in western Pacific region, and improved positive bias of outgoing shortwave radiation over the ocean. The new scheme also simulated better features of convectively coupled equatorial waves and Madden-Julian oscillation. These improvements were found to be derived from the modification of parameterization for the entrainment rate, i.e., the proposed parameterization suppressed excessive increase of entrainment, thus suppressing excessive increase of low-level clouds.

Alignment of time-resolved data from high throughput experiments.

Science.gov (United States)

Abidi, Nada; Franke, Raimo; Findeisen, Peter; Klawonn, Frank

2016-12-01

To better understand the dynamics of the underlying processes in cells, it is necessary to take measurements over a time course. Modern high-throughput technologies are often used for this purpose to measure the behavior of cell products like metabolites, peptides, proteins, [Formula: see text]RNA or mRNA at different points in time. Compared to classical time series, the number of time points is usually very limited and the measurements are taken at irregular time intervals. The main reasons for this are the costs of the experiments and the fact that the dynamic behavior usually shows a strong reaction and fast changes shortly after a stimulus and then slowly converges to a certain stable state. Another reason might simply be missing values. It is common to repeat the experiments and to have replicates in order to carry out a more reliable analysis. The ideal assumptions that the initial stimulus really started exactly at the same time for all replicates and that the replicates are perfectly synchronized are seldom satisfied. Therefore, there is a need to first adjust or align the time-resolved data before further analysis is carried out. Dynamic time warping (DTW) is considered as one of the common alignment techniques for time series data with equidistant time points. In this paper, we modified the DTW algorithm so that it can align sequences with measurements at different, non-equidistant time points with large gaps in between. This type of data is usually known as time-resolved data characterized by irregular time intervals between measurements as well as non-identical time points for different replicates. This new algorithm can be easily used to align time-resolved data from high-throughput experiments and to come across existing problems such as time scarcity and existing noise in the measurements. We propose a modified method of DTW to adapt requirements imposed by time-resolved data by use of monotone cubic interpolation splines. Our presented approach

Resolving the Spatial Structures of Bound Hole States in Black Phosphorus.

Science.gov (United States)

Qiu, Zhizhan; Fang, Hanyan; Carvalho, Alexandra; Rodin, A S; Liu, Yanpeng; Tan, Sherman J R; Telychko, Mykola; Lv, Pin; Su, Jie; Wang, Yewu; Castro Neto, A H; Lu, Jiong

2017-11-08

Understanding the local electronic properties of individual defects and dopants in black phosphorus (BP) is of great importance for both fundamental research and technological applications. Here, we employ low-temperature scanning tunnelling microscope (LT-STM) to probe the local electronic structures of single acceptors in BP. We demonstrate that the charge state of individual acceptors can be reversibly switched by controlling the tip-induced band bending. In addition, acceptor-related resonance features in the tunnelling spectra can be attributed to the formation of Rydberg-like bound hole states. The spatial mapping of the quantum bound states shows two distinct shapes evolving from an extended ellipse shape for the 1s ground state to a dumbbell shape for the 2p x excited state. The wave functions of bound hole states can be well-described using the hydrogen-like model with anisotropic effective mass, corroborated by our theoretical calculations. Our findings not only provide new insight into the many-body interactions around single dopants in this anisotropic two-dimensional material but also pave the way to the design of novel quantum devices.

Cation-Size-Dependent Conformational Locking of Glutamic Acid by Alkali Ions: Infrared Photodissociation Spectroscopy of Cryogenic Ions.

Science.gov (United States)

Klyne, Johanna; Bouchet, Aude; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Dopfer, Otto

2018-03-01

Consolidated knowledge of conformation and stability of amino acids and their clusters is required to understand their biochemical recognition. Often, alkali ions interact with amino acids and proteins. Herein, infrared photodissociation (IRPD) spectra of cryogenic metalated glutamic acid ions (GluM + , M = Li-Cs) are systematically analyzed in the isomer-specific fingerprint and XH stretch ranges (1100-1900, 2600-3600 cm -1 ) to provide a direct measure for cation-size-dependent conformational locking. GluM + ions are generated by electrospray ionization and cooled down to 15 K in a cryogenic quadrupole ion trap. The assignment of the IRPD spectra is supported by density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level. In the global minimum of GluM + , the flexibility of Glu is strongly reduced by the formation of rigid ionic CO···M + ···OC metal bridges, corresponding to charge solvation. The M + binding energy decreases monotonically with increasing cation size from D 0 = 314 to 119 kJ/mol for Li-Cs. Whereas for Li and Na only the global minimum of GluM + is observed, for K-Cs at least three isomers exist at cryogenic temperature. The IRPD spectra of cold GluM + ions are compared to IR multiple-photon dissociation spectra measured at room temperature. Furthermore, we elucidate the differences of the impact of protonation and metalation on the structure and conformational locking of Glu.

Thermochemical nonequilibrium analysis of O2+Ar based on state-resolved kinetics

International Nuclear Information System (INIS)

Kim, Jae Gang; Boyd, Iain D.

2015-01-01

Highlights: • Thermochemical nonequilibrium studies for three lowest lying electronic states of O 2 . • The complete sets of the rovibrational state-to-state transition rates of O 2 +Ar. • Rovibrational relaxations and coupled chemical reactions of O 2 . • Nonequilibrium reaction rates of O 2 derived from the quasi-steady state assumption. - Abstract: The thermochemical nonequilibrium of the three lowest lying electronic states of molecular oxygen, O 2 (X 3 Σ g - ,a 1 Δ g ,b 1 Σ g + ), through interactions with argon is studied in the present work. The multi-body potential energy surfaces of O 2 +Ar are evaluated from the semi-classical RKR potential of O 2 in each electronic state. The rovibrational states and energies of each electronic state are calculated by the quantum mechanical method based on the present inter-nuclear potential of O 2 . Then, the complete sets of the rovibrational state-to-state transition rate coefficients of O 2 +Ar are calculated by the quasi-classical trajectory method including the quasi-bound states. The system of master equations constructed by the present state-to-state transition rate coefficients are solved to analyze the thermochemical nonequilibrium of O 2 +Ar in various heat bath conditions. From these studies, it is concluded that the vibrational relaxation and coupled chemical reactions of each electronic state needs to be treated as a separate nonequilibrium process, and rotational nonequilibrium needs to be considered at translational temperatures above 10,000 K

Spatially-resolved measurement of optically stimulated luminescence and time-resolved luminescence

International Nuclear Information System (INIS)

Bailiff, I.K.; Mikhailik, V.B.

2003-01-01

Spatially-resolved measurements of optically stimulated luminescence (OSL) were performed using a two-dimensional scanning system designed for use with planar samples. The scanning system employs a focused laser beam to stimulate a selected area of the sample, which is moved under the beam by a motorised stage. Exposure of the sample is controlled by an electronic shutter. Mapping of the distribution of OSL using a continuous wave laser source was obtained with sub-millimeter resolution for samples of sliced brick, synthetic single crystal quartz, concrete and dental ceramic. These revealed sporadic emission in the case of brick or concrete and significant spatial variation of emission for quartz and dental ceramic slices. Determinations of absorbed dose were performed for quartz grains within a slice of modern brick. Reconfiguration of the scanner with a pulsed laser source enabled quartz and feldspathic minerals within a ceramic sample to be thinner region. about 6 nm from the extrapolation of themeasuring the time-resolved luminescence spectrum

Ultrafast time-resolved spectroscopy of the light-harvesting complex 2 (LH2) from the photosynthetic bacterium Thermochromatium tepidum.

Science.gov (United States)

Niedzwiedzki, Dariusz M; Fuciman, Marcel; Kobayashi, Masayuki; Frank, Harry A; Blankenship, Robert E

2011-10-01

The light-harvesting complex 2 from the thermophilic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption and fluorescence, sub-nanosecond-time-resolved fluorescence and femtosecond time-resolved transient absorption spectroscopy. The measurements were performed at room temperature and at 10 K. The combination of both ultrafast and steady-state optical spectroscopy methods at ambient and cryogenic temperatures allowed the detailed study of carotenoid (Car)-to-bacteriochlorophyll (BChl) as well BChl-to-BChl excitation energy transfer in the complex. The studies show that the dominant Cars rhodopin (N=11) and spirilloxanthin (N=13) do not play a significant role as supportive energy donors for BChl a. This is related with their photophysical properties regulated by long π-electron conjugation. On the other hand, such properties favor some of the Cars, particularly spirilloxanthin (N=13) to play the role of the direct quencher of the excited singlet state of BChl. © Springer Science+Business Media B.V. 2011

Electronic structure of charge-density-wave state in quasi-2D KMo6O17 purple bronze characterized by angle resolved photoemission spectroscopy

Science.gov (United States)

Valbuena, M. A.; Avila, J.; Drouard, S.; Guyot, H.; Asensio, M. C.

2006-01-01

We report on an angle-resolved-photoemission spectroscopy (ARPES) investigation of layered quasi-two dimensional (2D) Molybdenum purple bronze KMo6O17 in order to study and characterizes the transition to a charge-density-wave (CDW) state. We have performed photoemission temperature dependent measurements cooling down from room temperature (RT) to 32 K, well below the Peierls transition for this material, with CDW transition temperature Tc =110 K. The spectra have been taken at a selected kF point of the Fermi surface (FS) that satisfies the nesting condition of the FS, looking for the characteristic pseudo-gap opening in this kind of materials. The pseudogap has been estimated and it result to be in agreement with our previous works. The shift to lower binding energy of crossing Fermi level ARPES feature have been also confirmed and studied as a function of temperature, showing a rough like BCS behaviour. Finally we have also focused on ARPES measurements along ΓM¯ high symmetry direction for both room and low temperature states finding some insight for ‘shadow’ or back folded bands indicating the new periodicity of real lattice after the CDW lattice distortion.

OH+ emission from cometary knots in planetary nebulae

Science.gov (United States)

Priestley, F. D.; Barlow, M. J.

2018-05-01

We model the molecular emission from cometary knots in planetary nebulae (PNe) using a combination of photoionization and photodissociation region (PDR) codes, for a range of central star properties and gas densities. Without the inclusion of ionizing extreme ultraviolet (EUV) radiation, our models require central star temperatures T* to be near the upper limit of the range investigated in order to match observed H2 and OH+ surface brightnesses consistent with observations - with the addition of EUV flux, our models reproduce observed OH+ surface brightnesses for T* ≥ 100 kK. For T* non-detection of this molecule in PNe with such central star temperatures. Our predicted level of H2 emission is somewhat weaker than commonly observed in PNe, which may be resolved by the inclusion of shock heating or fluorescence due to UV photons. Some of our models also predict ArH+ and HeH+ rotational line emission above detection thresholds, despite neither molecule having been detected in PNe, although the inclusion of photodissociation by EUV photons, which is neglected by our models, would be expected to reduce their detectability.

48 CFR 29.101 - Resolving tax problems.

Science.gov (United States)

2010-10-01

.... (d) Before purchasing goods or services from a foreign source, the contracting officer should consult... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Resolving tax problems. 29... CONTRACTING REQUIREMENTS TAXES General 29.101 Resolving tax problems. (a) Contract tax problems are...

Picosecond rotationally resolved stimulated emission pumping spectroscopy of nitric oxide

International Nuclear Information System (INIS)

Tanjaroon, Chakree; Reeve, Scott W.; Ford, Alan; Murry, W. Dean; Lyon, Kevin; Yount, Bret; Britton, Dan; Burns, William A.; Allen, Susan D.; Bruce Johnson, J.

2012-01-01

Highlights: ► Stimulated emission pumping for nitric oxide was studied using picosecond lasers. ► Weak and tightly focused pulses provide sufficient energy for population transfer. ► Selective excitation at the bandhead yields strong fluorescence depletion signals. ► We observe 19% population transfer to v″ = 2 of the X 2 Π 1/2 ground electronic state. - Abstract: Stimulated emission pumping (SEP) experiments were performed on the nitric oxide molecule in a flow cell environment using lasers with pulse widths of 17–25 ps. A lambda excitation scheme, or ‘‘pump–dump” arrangement, was employed with the pump laser tuned to the T 00 vibronic band origin (λ pump =226.35(1)nm) of the A 2 Σ + (v′ = 0, J′) ← X 2 Π 1/2 (v″ = 0, J″) and the dump laser scanned from 246–248 nm within the A 2 Σ + (v′ = 0, J′) → X 2 Π 1/2 (v″ = 2, J″) transition. The rotationally resolved SEP spectra were measured by observing the total fluorescence within the A 2 Σ + (v′ = 0, J′) → X 2 Π 1/2 (v″ = 1, J″) transition between 235 nm and 237.2 nm while scanning the dump laser wavelengths. Multiple rotational states were excited due to the broad laser bandwidth. Measurements showed that the resolved rotational structure depended on the energy and bandwidth of the applied pump and dump laser pulses. Analysis of the observed fluorescence depletion signals yielded an average percent fluorescence depletion of about 19% when λ pump =226.35(1)nm and λ dump =247.91(1)nm. This value reflects the percent transfer of the NO population from the A 2 Σ + (V′ = 0, J′) excited electronic state to the X 2 Π 1/2 (v″ = 2, J″) ground electronic state. The maximum expected depletion is 50% in the limit of dump saturation. Selective excitation of NO at the bandhead provides good spectral discrimination from the background emission and noise and unambiguously confirms the identity of the emitter.

Transient analysis for resolving safety issues

International Nuclear Information System (INIS)

Chao, J.; Layman, W.

1987-01-01

The Nuclear Safety Analysis Center (NSAC) has a Generic Safety Analysis Program to help resolve high priority generic safety issues. This paper describes several high priority safety issues considered at NSAC and how they were resolved by transient analysis using thermal hydraulics and neutronics codes. These issues are pressurized thermal shock (PTS), anticipated transients without scram (ATWS), steam generator tube rupture (SGTR), and reactivity transients in light of the Chernobyl accident

Angle-resolved photoemission spectroscopy on iron-chalcogenide superconductors

Energy Technology Data Exchange (ETDEWEB)

Maletz, Janek; Zabolotnyy, Volodymyr; Evtushinsky, Daniil; Thirupathaiah, Setti; Wolter-Giraud, Anja; Harnagea, Luminita; Kordyuk, Alexander; Borisenko, Sergey [IFW Dresden (Germany); Yaresko, Alexander [MPI-FKF, Stuttgart (Germany); Vasiliev, Alexander [Moscow State University (Russian Federation); Chareev, Dimitri [RAS, Chernogolovka (Russian Federation); Rienks, Emile [Helmholtz-Zentrum Berlin (Germany); Buechner, Bernd [IFW Dresden (Germany); TU Dresden (Germany); Shermadini, Zurab; Luetkens, Hubertus; Sedlak, Kamil; Khasanov, Rustem; Amato, Alex; Krzton-Maziopa, Anna; Conder, Kazimierz; Pomjakushina, Ekaterina [Paul Scherrer Institute (Switzerland); Klauss, Hans-Henning [TU Dresden (Germany)

2014-07-01

The electronic structure of the iron chalcogenide superconductors FeSe{sub 1-x} and Rb{sub 0.77}Fe{sub 1.61}Se{sub 2} was investigated by high-resolution angle-resolved photoemission spectroscopy (ARPES). The results were compared to DFT calculations and μSR measurements. Both compounds share ''cigar-shaped'' Fermi surface sheets in their electronic structure, that can be found in almost all iron-pnictide superconductors. These features originate from a strong interplay of two hole- and electron-like bands in the Brillouin zone center, leading to a pronounced singularity in the density of states just below the Fermi level. This facilitates the coupling to a bosonic mode responsible for superconductivity.

A review of the analysis of complex time-resolved fluorescence anisotropy data

International Nuclear Information System (INIS)

Smith, Trevor A; Ghiggino, Kenneth P

2015-01-01

Time-resolved fluorescence anisotropy measurements (TRAMs) are widely used to probe the dynamics of the various processes that can lead to the depolarisation of emission following photoselection by polarised excitation. The most commonly investigated of these emission depolarising phenomena is molecular rotational motion, but TRAMs are very useful for determining the kinetics of a host of other processes. In this paper we review several examples for which we have observed in our laboratories initially unexpectedly complex temporal behaviour of the time-resolved fluorescence anisotropy signal from relatively ‘simple’ chemical systems. In certain circumstances the anisotropy (i) decays on timescales when superficially it might be thought it should remain constant, (ii) shows marked ‘dip and rise’ behaviour in its intensity, or (iii) can change sign as the anisotropy evolves in time. Fundamentally simple processes, including molecular rotational motion, energy migration and excited state photophysics, can cause such behaviour. (topical review)

Enforcement actions: Significant actions resolved

International Nuclear Information System (INIS)

1990-05-01

This compilation summarizes significant enforcement actions that have been resolved during one quarterly period (January--March 1990) and includes copies of letters, Notices, and Orders sent by the Nuclear Regulatory Commission to licensees with respect to these enforcement actions. Also included are a number of enforcement actions that had been previously resolved but not published in this NUREG. It is anticipated that the information in this publication will be widely disseminated to managers and employees engaged in activities licensed by the NRC, so that actions can be taken to improve safety by avoiding future violations similar to those described in this publication

Enforcement actions: Significant actions resolved

International Nuclear Information System (INIS)

1989-06-01

This compilation summarizes significant enforcement actions that have been resolved during one quarterly period (January--March 1989) and includes copies of letters, Notices, and Orders sent by the Nuclear Regulatory Commission to licensees with respect to these enforcement actions. Also included are a number of enforcement actions that had been previously resolved but not published in this NUREG. It is anticipated that the information in this publication will be widely disseminated to managers and employees engaged in activities licensed by the NRC, so that actions can be taken to improve safety by avoiding future violations similar to those described in this publication

Thermo-oxidative degradation study of melt-processed polyethylene and its blend with polyamide using time-resolved rheometry

CSIR Research Space (South Africa)

Salehiyan, Reza

2017-05-01

Full Text Available Time-resolved mechanical spectroscopy (TRMS) was conducted to study the thermo-oxidative degradation of linear low density polyethylene (LLDPE) samples with different thermal histories and their blends with a polyamide (PA6) in the melt state. Neat...

Photoelectron spectra of N2+: Rotational line profiles studied with HeI-excited angle-resolved spectroscopy and with synchrotron radiation

International Nuclear Information System (INIS)

Ohrwall, G.; Baltzer, P.; Bozek, J.

2004-01-01

We have recorded angle-resolved He I photoelectron spectra of the three outer most valence states in N+2, with high enough resolution to observe rotational line profiles. For the two Sigma states, the X 2 Sigma +g and the B 2 Sigma +u, we found that the rotational branches corresponding to different changes in rotational quantum number can differ dramatically in beta value. The well-known difference in beta value for the nu=0 and nu =1 vibrations of the X 2 Sigma +g state was found to be due to different rotational branching ratios and also different beta values of the rotational branches. For the nu=0-2 vibrations of the A 2 Pi u state, the beta value difference between rotational branches is much less pronounced than in the X and B states. We have also recorded synchrotron-radiation-excited photoelectron spectra of the nu=0 vibrational peaks of the X 2 Sigma +g and B 2 Sigma +u states where rotational line profiles are resolved. The intensities of the rotational branches were studied as function of photon energy, the X state between 23 and 65 eV, and We have recorded angle-resolved He I photoelectron spectra of the three outermost valence states in N+2, with high enough resolution to observe rotational line profiles. For the two Sigma states, the X 2 Sigma +g and the B 2 Sigma +u, we found that the rotational branches corresponding to different changes in rotational quantum number can differ dramatically in beta value. The well-known difference in beta value for the nu=0 and nu=1 vibrations of the X 2 Sigma +g state was found to be due to different rotational branching ratios and also different beta values of the rotational branches. For the nu=0-2 vibrations of the A 2 Pi u state, the beta value difference between rotational branches is much less pronounced than in the X and B states. We have also recorded synchrotron-radiation-excited photoelectron spectra of the nu=0 vibrational peaks of the X 2 Sigma +g and B 2 Sigma +u states where rotational line profiles a

Time-resolved pump-probe X-ray absorption fine structure spectroscopy of Gaq3

International Nuclear Information System (INIS)

Dicke, Benjamin

2013-01-01

Gallium(tris-8-hydroxyquinoline) (Gaq 3 ) belongs to a class of metal organic compounds, used as electron transport layer and emissive layer in organic light emitting diodes. Many research activities have concentrated on the optical and electronic properties, especially of the homologue molecule aluminum(tris-8-hydroxyquinoline) (Alq 3 ). Knowledge of the first excited state S 1 structure of these molecules could provide deeper insight into the processes involved into the operation of electronic devices, such as OLEDs and, hence, it could further improve their efficiency and optical properties. Until now the excited state structure could not be determined experimentally. Most of the information about this structure mainly arises from theoretical calculations. X-ray absorption fine structure (XAFS) spectroscopy is a well developed technique to determine both, the electronic and the geometric properties of a sample. The connection of ultrashort pulsed X-ray sources with a pulsed laser system offers the possibility to use XAFS as a tool for studying the transient changes of a sample induced by a laser pulse. In the framework of this thesis a new setup for time-resolved pump-probe X-ray absorption spectroscopy at PETRA III beamline P11 was developed for measuring samples in liquid form. In this setup the sample is pumped into its photo-excited state by a femtosecond laser pump pulse with 343 nm wavelength and after a certain time delay probed by an X-ray probe pulse. In this way the first excited singlet state S 1 of Gaq 3 dissolved in benzyl alcohol was analyzed. A structural model for the excited state structure of the Gaq 3 molecule based on the several times reproduced results of the XAFS experiments is proposed. According to this model it was found that the Ga-N A bond length is elongated, while the Ga-O A bond length is shortened upon photoexcitation. The dynamics of the structural changes were not the focus of this thesis. Nevertheless the excited state lifetime

A phenomenological theory of the pseudogap state

International Nuclear Information System (INIS)

Rice, T.M.; Yang Kaiyu; Zhang Fuchun

2007-01-01

An ansatz is proposed for the coherent part of the single particle Green's function in a doped resonant valence bond (RVB) state by analogy with the form derived by Konik and coworkers for an array of 2-leg Hubbard ladders near half-filling. The parameters of the RVB state are taken from the renormalized mean field theory of Zhang and coworkers for underdoped cuprates. The ansatz shows good agreement with recent angle resolved photoemission on underdoped cuprates and resolves an apparent disagreement with the Luttinger sum rule

Photodissociation of C{sub 3}H{sub 5}Br and C{sub 4}H{sub 7}Br at 234 nm

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Kook; Paul, Dababrata; Hong, Ki Ryong; Cho, Ha Na; Kim, Tae Kyu [Pusan National University, Busan (Korea, Republic of); Lee, Kyoung Seok [Korea Research Institute of Standards and Science, Daejeon (Korea, Republic of)

2012-01-15

The photodissociation dynamics of cyclopropyl bromide (C-3H{sub 5}Br) and cyclobutyl bromide (C{sub 4}H{sub 7}Br) at 234 nm was investigated. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br({sup 2}P{sub 3/2}) and Br*({sup 2}P{sub 1/2}) atoms. The recoil anisotropies for the Br and Br* channels were measured to be βBr = 0.92 ± 0.03 and βBr* = 1.52 ± 0.04 for C{sub 3}H{sub 5}Br and βBr = 1.10 ± 0.03 and βBr* = 1.49 ± 0.05 for C{sub 4}H{sub 7}Br. The relative quantum yield for Br was found to be ΦBr = 0.13 ± 0.03 and for C{sub 3}H{sub 5}Br and C{sub 4}H{sub 7}Br, respectively. The soft radical limit of the impulsive model adequately modeled the related energy partitioning. The nonadiabatic transition probability from the 3A' and 4A' potential energy surfaces was estimated and discussed.

48 CFR 30.606 - Resolving cost impacts.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Resolving cost impacts. 30... impacts. (a) General. (1) The CFAO shall coordinate with the affected contracting officers before negotiating and resolving the cost impact when the estimated cost impact on any of their contracts is at least...

Evidence for concerted ring opening and C–Br bond breaking in UV-excited bromocyclopropane

Energy Technology Data Exchange (ETDEWEB)

Pandit, Shubhrangshu; Preston, Thomas J.; Orr-Ewing, Andrew J., E-mail: a.orr-ewing@bristol.ac.uk [School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS (United Kingdom); King, Simon J.; Vallance, Claire [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford OX1 3TA (United Kingdom)

2016-06-28

Photodissociation of gaseous bromocyclopropane via its A-band continuum has been studied at excitation wavelengths ranging from 230 nm to 267 nm. Velocity-map images of ground-state bromine atoms (Br), spin-orbit excited bromine atoms (Br{sup ∗}), and C{sub 3}H{sub 5} hydrocarbon radicals reveal the kinetic energies of these various photofragments. Both Br and Br{sup ∗} atoms are predominantly generated via repulsive excited electronic states in a prompt photodissociation process in which the hydrocarbon co-fragment is a cyclopropyl radical. However, the images obtained at the mass of the hydrocarbon radical fragment identify a channel with total kinetic energy greater than that deduced from the Br and Br{sup ∗} images, and with a kinetic energy distribution that exceeds the energetic limit for Br + cyclopropyl radical products. The velocity-map images of these C{sub 3}H{sub 5} fragments have lower angular anisotropies than measured for Br and Br{sup ∗}, indicating molecular restructuring during dissociation. The high kinetic energy C{sub 3}H{sub 5} signals are assigned to allyl radicals generated by a minor photochemical pathway which involves concerted C–Br bond dissociation and cyclopropyl ring-opening following single ultraviolet (UV)-photon absorption. Slow photofragments also contribute to the velocity map images obtained at the C{sub 3}H{sub 5} radical mass, but the corresponding slow Br atoms are not observed. These features in the images are attributed to C{sub 3}H{sub 5}{sup +} from the photodissociation of the C{sub 3}H{sub 5}Br{sup +} molecular cation following two-photon ionization of the parent compound. This assignment is confirmed by 118-nm vacuum ultraviolet ionization studies that prepare the molecular cation in its ground electronic state prior to UV photodissociation.

The conforming brain and deontological resolve.

Science.gov (United States)

Pincus, Melanie; LaViers, Lisa; Prietula, Michael J; Berns, Gregory

2014-01-01

Our personal values are subject to forces of social influence. Deontological resolve captures how strongly one relies on absolute rules of right and wrong in the representation of one's personal values and may predict willingness to modify one's values in the presence of social influence. Using fMRI, we found that a neurobiological metric for deontological resolve based on relative activity in the ventrolateral prefrontal cortex (VLPFC) during the passive processing of sacred values predicted individual differences in conformity. Individuals with stronger deontological resolve, as measured by greater VLPFC activity, displayed lower levels of conformity. We also tested whether responsiveness to social reward, as measured by ventral striatal activity during social feedback, predicted variability in conformist behavior across individuals but found no significant relationship. From these results we conclude that unwillingness to conform to others' values is associated with a strong neurobiological representation of social rules.

The conforming brain and deontological resolve.

Directory of Open Access Journals (Sweden)

Melanie Pincus

Full Text Available Our personal values are subject to forces of social influence. Deontological resolve captures how strongly one relies on absolute rules of right and wrong in the representation of one's personal values and may predict willingness to modify one's values in the presence of social influence. Using fMRI, we found that a neurobiological metric for deontological resolve based on relative activity in the ventrolateral prefrontal cortex (VLPFC during the passive processing of sacred values predicted individual differences in conformity. Individuals with stronger deontological resolve, as measured by greater VLPFC activity, displayed lower levels of conformity. We also tested whether responsiveness to social reward, as measured by ventral striatal activity during social feedback, predicted variability in conformist behavior across individuals but found no significant relationship. From these results we conclude that unwillingness to conform to others' values is associated with a strong neurobiological representation of social rules.

Watching proteins function with time-resolved x-ray crystallography

Energy Technology Data Exchange (ETDEWEB)

Šrajer, Vukica; Schmidt, Marius

2017-08-22

Macromolecular crystallography was immensely successful in the last two decades. To a large degree this success resulted from use of powerful third generation synchrotron x-ray sources. An expansive database of more than 100 000 protein structures, of which many were determined at resolution better than 2 Å, is available today. With this achievement, the spotlight in structural biology is shifting from determination of static structures to elucidating dynamic aspects of protein function. A powerful tool for addressing these aspects is time-resolved crystallography, where a genuine biological function is triggered in the crystal with a goal of capturing molecules in action and determining protein kinetics and structures of intermediates (Schmidt et al 2005a Methods Mol. Biol. 305 115–54, Schmidt 2008 Ultrashort Laser Pulses in Biology and Medicine (Berlin: Springer) pp 201–41, Neutze and Moffat 2012 Curr. Opin. Struct. Biol. 22 651–9, Šrajer 2014 The Future of Dynamic Structural Science (Berlin: Springer) pp 237–51). In this approach, short and intense x-ray pulses are used to probe intermediates in real time and at room temperature, in an ongoing reaction that is initiated synchronously and rapidly in the crystal. Time-resolved macromolecular crystallography with 100 ps time resolution at synchrotron x-ray sources is in its mature phase today, particularly for studies of reversible, light-initiated reactions. The advent of the new free electron lasers for hard x-rays (XFELs; 5–20 keV), which provide exceptionally intense, femtosecond x-ray pulses, marks a new frontier for time-resolved crystallography. The exploration of ultra-fast events becomes possible in high-resolution structural detail, on sub-picosecond time scales (Tenboer et al 2014 Science 346 1242–6, Barends et al 2015 Science 350 445–50, Pande et al 2016 Science 352 725–9). We review here state-of-the-art time-resolved crystallographic experiments both at synchrotrons and XFELs. We

Watching proteins function with time-resolved x-ray crystallography

International Nuclear Information System (INIS)

Šrajer, Vukica; Schmidt, Marius

2017-01-01

Macromolecular crystallography was immensely successful in the last two decades. To a large degree this success resulted from use of powerful third generation synchrotron x-ray sources. An expansive database of more than 100 000 protein structures, of which many were determined at resolution better than 2 Å, is available today. With this achievement, the spotlight in structural biology is shifting from determination of static structures to elucidating dynamic aspects of protein function. A powerful tool for addressing these aspects is time-resolved crystallography, where a genuine biological function is triggered in the crystal with a goal of capturing molecules in action and determining protein kinetics and structures of intermediates (Schmidt et al 2005a Methods Mol. Biol . 305 115–54, Schmidt 2008 Ultrashort Laser Pulses in Biology and Medicine (Berlin: Springer) pp 201–41, Neutze and Moffat 2012 Curr. Opin. Struct. Biol . 22 651–9, Šrajer 2014 The Future of Dynamic Structural Science (Berlin: Springer) pp 237–51). In this approach, short and intense x-ray pulses are used to probe intermediates in real time and at room temperature, in an ongoing reaction that is initiated synchronously and rapidly in the crystal. Time-resolved macromolecular crystallography with 100 ps time resolution at synchrotron x-ray sources is in its mature phase today, particularly for studies of reversible, light-initiated reactions. The advent of the new free electron lasers for hard x-rays (XFELs; 5–20 keV), which provide exceptionally intense, femtosecond x-ray pulses, marks a new frontier for time-resolved crystallography. The exploration of ultra-fast events becomes possible in high-resolution structural detail, on sub-picosecond time scales (Tenboer et al 2014 Science 346 1242–6, Barends et al 2015 Science 350 445–50, Pande et al 2016 Science 352 725–9). We review here state-of-the-art time-resolved crystallographic experiments both at synchrotrons and XFELs

A Turn-Projected State-Based Conflict Resolution Algorithm

Science.gov (United States)

Butler, Ricky W.; Lewis, Timothy A.

2013-01-01

State-based conflict detection and resolution (CD&R) algorithms detect conflicts and resolve them on the basis on current state information without the use of additional intent information from aircraft flight plans. Therefore, the prediction of the trajectory of aircraft is based solely upon the position and velocity vectors of the traffic aircraft. Most CD&R algorithms project the traffic state using only the current state vectors. However, the past state vectors can be used to make a better prediction of the future trajectory of the traffic aircraft. This paper explores the idea of using past state vectors to detect traffic turns and resolve conflicts caused by these turns using a non-linear projection of the traffic state. A new algorithm based on this idea is presented and validated using a fast-time simulator developed for this study.

Real-time visualization of the vibrational wavepacket dynamics in electronically excited pyrimidine via femtosecond time-resolved photoelectron imaging

Science.gov (United States)

Li, Shuai; Long, Jinyou; Ling, Fengzi; Wang, Yanmei; Song, Xinli; Zhang, Song; Zhang, Bing

2017-07-01

The vibrational wavepacket dynamics at the very early stages of the S1-T1 intersystem crossing in photoexcited pyrimidine is visualized in real time by femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. A coherent superposition of the vibrational states is prepared by the femtosecond pump pulse at 315.3 nm, resulting in a vibrational wavepacket. The composition of the prepared wavepacket is directly identified by a sustained quantum beat superimposed on the parent-ion transient, possessing a frequency in accord with the energy separation between the 6a1 and 6b2 states. The dephasing time of the vibrational wavepacket is determined to be 82 ps. More importantly, the variable Franck-Condon factors between the wavepacket components and the dispersed cation vibrational levels are experimentally illustrated to identify the dark state and follow the energy-flow dynamics on the femtosecond time scale. The time-dependent intensities of the photoelectron peaks originated from the 6a1 vibrational state exhibit a clear quantum beating pattern with similar periodicity but a phase shift of π rad with respect to those from the 6b2 state, offering an unambiguous picture of the restricted intramolecular vibrational energy redistribution dynamics in the 6a1/6b2 Fermi resonance.

High-throughput bioconjugation for enhanced 193 nm photodissociation via droplet phase initiated ion/ion chemistry using a front-end dual spray reactor.

Science.gov (United States)

Cotham, Victoria C; Shaw, Jared B; Brodbelt, Jennifer S

2015-09-15

Fast online chemical derivatization of peptides with an aromatic label for enhanced 193 nm ultraviolet photodissociation (UVPD) is demonstrated using a dual electrospray reactor implemented on the front-end of a linear ion trap (LIT) mass spectrometer. The reactor facilitates the intersection of protonated peptides with a second population of chromogenic 4-formyl-1,3-benzenedisulfonic acid (FBDSA) anions to promote real-time formation of ion/ion complexes at atmospheric pressure. Subsequent collisional activation of the ion/ion intermediate results in Schiff base formation generated via reaction between a primary amine in the peptide cation and the aldehyde moiety of the FBDSA anion. Utilizing 193 nm UVPD as the subsequent activation step in the MS(3) workflow results in acquisition of greater primary sequence information relative to conventional collision induced dissociation (CID). Furthermore, Schiff-base-modified peptides exhibit on average a 20% increase in UVPD efficiency compared to their unmodified counterparts. Due to the efficiency of covalent labeling achieved with the dual spray reactor, we demonstrate that this strategy can be integrated into a high-throughput LC-MS(n) workflow for rapid derivatization of peptide mixtures.

Energy-resolved attosecond interferometric photoemission from Ag(111) and Au(111) surfaces

Science.gov (United States)

Ambrosio, M. J.; Thumm, U.

2018-04-01

Photoelectron emission from solid surfaces induced by attosecond pulse trains into the electric field of delayed phase-coherent infrared (IR) pulses allows the surface-specific observation of energy-resolved electronic phase accumulations and photoemission delays. We quantum-mechanically modeled interferometric photoemission spectra from the (111) surfaces of Au and Ag, including background contributions from secondary electrons and direct emission by the IR pulse, and adjusted parameters of our model to energy-resolved photoelectron spectra recently measured at a synchrotron light source by Roth et al. [J. Electron Spectrosc. 224, 84 (2018), 10.1016/j.elspec.2017.05.008]. Our calculated spectra and photoelectron phase shifts are in fair agreement with the experimental data of Locher et al. [Optica 2, 405 (2015), 10.1364/OPTICA.2.000405]. Our model's not reproducing the measured energy-dependent oscillations of the Ag(111) photoemission phases may be interpreted as evidence for subtle band-structure effects on the final-state photoelectron-surface interaction not accounted for in our simulation.

Stimulated emission depletion microscopy resolves individual nitrogen vacancy centers in diamond nanocrystals.

Science.gov (United States)

Arroyo-Camejo, Silvia; Adam, Marie-Pierre; Besbes, Mondher; Hugonin, Jean-Paul; Jacques, Vincent; Greffet, Jean-Jacques; Roch, Jean-François; Hell, Stefan W; Treussart, François

2013-12-23

Nitrogen-vacancy (NV) color centers in nanodiamonds are highly promising for bioimaging and sensing. However, resolving individual NV centers within nanodiamond particles and the controlled addressing and readout of their spin state has remained a major challenge. Spatially stochastic super-resolution techniques cannot provide this capability in principle, whereas coordinate-controlled super-resolution imaging methods, like stimulated emission depletion (STED) microscopy, have been predicted to fail in nanodiamonds. Here we show that, contrary to these predictions, STED can resolve single NV centers in 40-250 nm sized nanodiamonds with a resolution of ≈10 nm. Even multiple adjacent NVs located in single nanodiamonds can be imaged individually down to relative distances of ≈15 nm. Far-field optical super-resolution of NVs inside nanodiamonds is highly relevant for bioimaging applications of these fluorescent nanolabels. The targeted addressing and readout of individual NV(-) spins inside nanodiamonds by STED should also be of high significance for quantum sensing and information applications.

Time-resolved protein nano-crystallography using an X-ray free-electron laser

International Nuclear Information System (INIS)

Aquila, Andrew; Hunter, Mark S.; Fromme, Petra; Fromme, Raimund; Grotjohann, Ingo; Doak, R. Bruce; Kirian, Richard A.; Schmidt, Kevin E.; Wang, Xiaoyu; Weierstall, Uwe; Spence, John C.H.; White, Thomas A.; Caleman, Carl; DePonte, Daniel P.; Fleckenstein, Holger; Gumprecht, Lars; Liang, Mengning; Martin, Andrew V.; Schulz, Joachim; Stellato, Francesco; Stern, Stephan; Barty, Anton; Andreasson, Jakob; Davidsson, Jan; Hajdu, Janos; Maia, Filipe R.N.C.; Seibert, M. Marvin; Timneanu, Nicusor; Arnlund, David; Johansson, Linda; Malmerberg, Erik; Neutze, Richard; Bajt, Sasa; Barthelmess, Miriam; Graafsma, Heinz; Hirsemann, Helmut; Wunderer, Cornelia; Barends, Thomas R.M.; Foucar, Lutz; Krasniqi, Faton; Lomb, Lukas; Rolles, Daniel; Schlichting, Ilme; Schmidt, Carlo; Bogan, Michael J.; Hampton, Christina Y.; Sierra, Raymond; Starodub, Dmitri; Bostedt, Christoph; Bozek, John D.; Messerschmidt, Marc; Williams, Garth J.; Bottin, Herve

2012-01-01

We demonstrate the use of an X-ray free electron laser synchronized with an optical pump laser to obtain X-ray diffraction snapshots from the photo-activated states of large membrane protein complexes in the form of nano-crystals flowing in a liquid jet. Light-induced changes of Photosystem I-Ferredoxin co-crystals were observed at time delays of 5 to 10 μs after excitation. The result correlates with the microsecond kinetics of electron transfer from Photosystem I to ferredoxin. The undocking process that follows the electron transfer leads to large rearrangements in the crystals that will terminally lead to the disintegration of the crystals. We describe the experimental setup and obtain the first time resolved femtosecond serial X-ray crystallography results from an irreversible photo-chemical reaction at the Linac Coherent Light Source. This technique opens the door to time-resolved structural studies of reaction dynamics in biological systems. (authors)

Resolving Ethical Dilemmas in Financial Audit

OpenAIRE

Professor PhD Turlea Eugeniu; PhD Student Mocanu Mihaela

2010-01-01

Resolving ethical dilemmas is a difficult endeavor in any field and financial auditing makes no exception. Ethical dilemmas are complex situations which derive from a conflict and in which a decision among several alternatives is needed. Ethical dilemmas are common in the work of the financial auditor, whose mission is to serve the interests of the public at large, not those of the auditee’s managers who mandate him/her. The objective of the present paper is to offer support in resolving ethi...

Energy- and time-resolved microscopy using PEEM: recent developments and state-of-the-art

Energy Technology Data Exchange (ETDEWEB)

Weber, N B; Escher, M; Merkel, M [FOCUS GmbH, Neukirchner Strasse 2, 65510 Huenstetten (Germany); Oelsner, A [Surface Concept GmbH, Staudingerweg 7, 55099 Mainz (Germany); Schoenhense, G [Johannes Gutenberg Universitaet, Institut fuer Physik, 55099 Mainz (Germany)], E-mail: n.weber@focus-gmbh.com

2008-03-15

Two novel methods of spectroscopic surface imaging are discussed, both based on photoemission electron microscopy PEEM. They are characterised by a simple electron-optical set up retaining a linear column. An imaging high-pass energy filter has been developed on the basis of lithographically-fabricated microgrids. Owing to a mesh size of only 7{mu}m, no image distortions occur. The present energy resolution is 70 meV. The second approach employs time-of-flight energy dispersion and time-resolved detection using a Delayline Detector. In this case, the drift energy and the time resolution of the detector determine the energy resolution. The present time resolution is 180 ps, giving rise to an energy resolution in the 100 meV range.

Theoretical Concepts in Molecular Photodissociation Dynamics

DEFF Research Database (Denmark)

Henriksen, Niels Engholm

1995-01-01

This chapter contains sections titled: Introduction Quantum Dynamics of Molecular Photofragmentation The Total Reaction Probability Final Product Distributions Time-Independent Approach, Stationary Scattering States Gaussian Wave Packet Dynamics Wigner Phase Space Representation The Diatomic...

Spatially resolved spectroscopy on semiconductor nanostructures

Energy Technology Data Exchange (ETDEWEB)

Roessler, Johanna

2009-02-20

Cleared edge overgrowth (CEO) nanostructures are identified and studied by 1D und 2D {mu}PL mapping scans and by time-resolved and power-dependent measurements. Distinct excitonic ground states of 2fold CEO QDs with large localization energies are achieved. The deeper localization reached as compared to the only other report on 2fold CEO QDs in literature is attributed to a new strain-free fabrication process and changed QW thickness in [001] growth. In order to achieve controlled manipulation of 2fold CEO QDs the concept of a CEO structure with three top gates and one back gate is presented. Due to the complexity of this device, a simpler test structure is realized. Measurements on this test structure confirm the necessity to either grow significantly thicker overgrowth layers or to provide separate top gates in all three spatial direction to controllably manipulate 2fold CEO QDs with an external electric field. (orig.)

Super-resolved terahertz microscopy by knife-edge scan

Science.gov (United States)

Giliberti, V.; Flammini, M.; Ciano, C.; Pontecorvo, E.; Del Re, E.; Ortolani, M.

2017-08-01

We present a compact, all solid-state THz confocal microscope operating at 0.30 THz that achieves super-resolution by using the knife-edge scan approach. In the final reconstructed image, a lateral resolution of 60 μm ≍ λ/17 is demonstrated when the knife-edge is deep in the near-field of the sample surface. When the knife-edge is lifted up to λ/4 from the sample surface, a certain degree of super-resolution is maintained with a resolution of 0.4 mm, i.e. more than a factor 2 if compared to the diffraction-limited scheme. The present results open an interesting path towards super-resolved imaging with in-depth information that would be peculiar to THz microscopy systems.

Life-time resolved emission spectra in CdI2 crystals

International Nuclear Information System (INIS)

Kawabata, Seiji; Nakagawa, Hideyuki

2007-01-01

The emission spectrum of CdI 2 is composed of ultraviolet (UV), green (G) and yellow (Y and Y') bands peaking at 3.38, 2.50, 2.16 and 2.25 eV, respectively. In order to determine the initial states of the Y- and G-luminescence, decay curves have been measured at 6 and 80 K by varying emission energy. The observed decay curves are composed of two or three exponential components. These decay components were named τ 1 , τ 2 , τ 3 , τ 3' and τ 4 . The emission spectrum for each decay component, i.e., the life-time resolved emission spectrum, was constructed from the observed decay curves. At 6 K, three bands at 2.12, 2.49 and 2.64 eV are obtained for τ 1 , τ 2 and τ 3 components, respectively. At 80 K, a dominant band for the τ 4 component and a weak band for the τ 3' component appear on the same energy position at 2.25 eV. The origin of each emission band in the life-time resolved emission spectra will be briefly discussed

Ultrafast excited-state relaxation of a binuclear Ag(i) phosphine complex in gas phase and solution.

Science.gov (United States)

Kruppa, S V; Bäppler, F; Klopper, W; Walg, S P; Thiel, W R; Diller, R; Riehn, C

2017-08-30

The binuclear complex [Ag 2 (dcpm) 2 ](PF 6 ) 2 (dcpm = bis(dicyclohexylphosphino)methane) exhibits a structure with a close silver-silver contact mediated by the bridging ligand and thus a weak argentophilic interaction. Upon electronic excitation this cooperative effect is strongly increased and determines the optical and luminescence properties of the compound. We have studied here the ultrafast electronic dynamics in parallel in gas phase by transient photodissociation and in solution by transient absorption. In particular, we report the diverse photofragmentation pathways of isolated [Ag 2 (dcpm) 2 ] 2+ in an ion trap and its gas phase UV photodissociation spectrum. By pump-probe fragmentation action spectroscopy (λ ex = 260 nm) in the gas phase, we have obtained fragment-specific transients which exhibit a common ultrafast multiexponential decay. This is fitted to four time constants (0.6/5.8/100/>1000 ps), highlighting complex intrinsic photophysical processes. Remarkably, multiexponential dynamics (0.9/8.5/73/604 ps) are as well found for the relaxation dynamics in acetonitrile solution. Ab initio calculations at the level of approximate coupled-cluster singles-doubles (CC2) theory of ground and electronically excited states of the reduced model system [Ag 2 (dmpm) 2 ] 2+ (dmpm = bis(dimethylphosphino)methane) indicate a shortening of the Ag-Ag distance upon excitation by 0.3-0.4 Å. In C 2 geometry two close-lying singlet states S 1 ( 1 MC(dσ*-pπ), 1 B, 4.13 eV) and S 2 ( 1 MC(dσ*-pσ), 1 A, 4.45 eV) are found. The nearly dark S 1 state has not been reported so far. The excitation of the S 2 state carries a large oscillator strength for the calculated vertical transition (266 nm). Two related triplets are calculated at T 1 (3.87 eV) and T 2 (3.90 eV). From these findings we suggest possible relaxation pathways with the two short time constants ascribed to ISC/IVR and propose from the obtained similar values in gas phase that the fast solution dynamics

Fine-structure resolved rotational transitions and database for CN+H2 collisions

Science.gov (United States)

Burton, Hannah; Mysliwiec, Ryan; Forrey, Robert C.; Yang, B. H.; Stancil, P. C.; Balakrishnan, N.

2018-06-01

Cross sections and rate coefficients for CN+H2 collisions are calculated using the coupled states (CS) approximation. The calculations are benchmarked against more accurate close-coupling (CC) calculations for transitions between low-lying rotational states. Comparisons are made between the two formulations for collision energies greater than 10 cm-1. The CS approximation is used to construct a database which includes highly excited rotational states that are beyond the practical limitations of the CC method. The database includes fine-structure resolved rotational quenching transitions for v = 0 and j ≤ 40, where v and j are the vibrational and rotational quantum numbers of the initial state of the CN molecule. Rate coefficients are computed for both para-H2 and ortho-H2 colliders. The results are shown to be in good agreement with previous calculations, however, the rates are substantially different from mass-scaled CN+He rates that are often used in astrophysical models.

Angle-resolved photoemission study and first-principles calculation of the electronic structure of LaSb2

International Nuclear Information System (INIS)

Acatrinei, Alice I; Browne, D; Losovyj, Y B; Young, D P; Moldovan, M; Chan, Julia Y; Sprunger, P T; Kurtz, Richard L

2003-01-01

In this work we present valence band studies of LaSb 2 using angle-resolved photoelectron spectroscopy with synchrotron radiation and compare these data with band structure calculations. Valence band spectra reveal that Sb 5p states are dominant near the Fermi level and are hybridized with the La 5d states just below. The calculations show a fair agreement with the experimentally determined valence band spectra, allowing an identification of the observed features. We measured some dispersion for kbar, especially for Sb 5p states; no significant dispersion was found for k || . (letter to the editor)

Time-resolved quantitative phosphoproteomics

DEFF Research Database (Denmark)

Verano-Braga, Thiago; Schwämmle, Veit; Sylvester, Marc

2012-01-01

proteins involved in the Ang-(1-7) signaling, we performed a mass spectrometry-based time-resolved quantitative phosphoproteome study of human aortic endothelial cells (HAEC) treated with Ang-(1-7). We identified 1288 unique phosphosites on 699 different proteins with 99% certainty of correct peptide...

[A new measurement method of time-resolved spectrum].

Science.gov (United States)

Shi, Zhi-gang; Huang, Shi-hua; Liang, Chun-jun; Lei, Quan-sheng

2007-02-01

A new method for measuring time-resolved spectrum (TRS) is brought forward. Programming with assemble language controlled the micro-control-processor (AT89C51), and a kind of peripheral circuit constituted the drive circuit, which drived the stepping motor to run the monochromator. So the light of different kinds of expected wavelength could be obtained. The optical signal was transformed to electrical signal by optical-to-electrical transform with the help of photomultiplier tube (Hamamatsu 1P28). The electrical signal of spectrum data was transmitted to the oscillograph. Connecting the two serial interfaces of RS232 between the oscillograph and computer, the electrical signal of spectrum data could be transmitted to computer for programming to draw the attenuation curve and time-resolved spectrum (TRS) of the swatch. The method for measuring time-resolved spectrum (TRS) features parallel measurement in time scale but serial measurement in wavelength scale. Time-resolved spectrum (TRS) and integrated emission spectrum of Tb3+ in swatch Tb(o-BBA)3 phen were measured using this method. Compared with the real time-resolved spectrum (TRS). It was validated to be feasible, credible and convenient. The 3D spectra of fluorescence intensity-wavelength-time, and the integrated spectrum of the swatch Tb(o-BBA)3 phen are given.

Numerical study of combustion initiation in a supersonic flow of H2-air mixture by resonance laser radiation

International Nuclear Information System (INIS)

Bezgin, L V; Kopchenov, V I; Kuleshov, P S; Titova, N S; Starik, A M

2012-01-01

A comparative analysis of the efficiency of approaches based on the exposure of reacting gas to resonance laser radiation to enhance combustion in a supersonic flow of H 2 -air mixture is conducted. The kinetic processes responsible for the intensification of chain reactions in premixed and non-premixed H 2 -air flows upon photodissociation of O 2 molecules by 193.3 nm laser radiation, excitation of these molecules to the singlet sigma state by laser photons with 762.346 nm wavelength and heating the mixture by laser radiation are analysed in a detailed manner. It is shown that both photochemical methods, photodissociation and excitation of O 2 molecules, are much more effective in shortening the ignition delay length than merely heating the mixture. For the premixed flow, the photodissociation of O 2 molecules ensures a slightly higher reduction in the ignition delay than the laser-induced excitation of molecular oxygen to the singlet sigma state. However, in the non-premixed flow the situation is inverted. The analysis shows that both photochemical methods make it possible to raise the efficiency of conversion of reactant chemical energy to thermal energy released during combustion compared with the method of heating the mixtures. (paper)

Time-resolved stimulated emission depletion and energy transfer dynamics in two-photon excited EGFP

Science.gov (United States)

Masters, T. A.; Robinson, N. A.; Marsh, R. J.; Blacker, T. S.; Armoogum, D. A.; Larijani, B.; Bain, A. J.

2018-04-01

Time and polarization-resolved stimulated emission depletion (STED) measurements are used to investigate excited state evolution following the two-photon excitation of enhanced green fluorescent protein (EGFP). We employ a new approach for the accurate STED measurement of the hitherto unmeasured degree of hexadecapolar transition dipole moment alignment ⟨α40 ⟩ present at a given excitation-depletion (pump-dump) pulse separation. Time-resolved polarized fluorescence measurements as a function of pump-dump delay reveal the time evolution of ⟨α40 ⟩ to be considerably more rapid than predicted for isotropic rotational diffusion in EGFP. Additional depolarization by homo-Förster resonance energy transfer is investigated for both ⟨α20 ⟩ (quadrupolar) and ⟨α40 ⟩ transition dipole alignments. These results point to the utility of higher order dipole correlation measurements in the investigation of resonance energy transfer processes.

Quantum state-resolved, bulk gas energetics: Comparison of theory and experiment

Energy Technology Data Exchange (ETDEWEB)

McCaffery, Anthony J., E-mail: A.J.McCaffery@sussex.ac.uk [Department of Chemistry, University of Sussex, Brighton, Sussex BN1 6SJ (United Kingdom)

2016-05-21

Until very recently, the computational model of state-to-state energy transfer in large gas mixtures, introduced by the author and co-workers, has had little experimental data with which to assess the accuracy of its predictions. In a novel experiment, Alghazi et al. [Chem. Phys. 448, 76 (2015)] followed the equilibration of highly vibrationally excited CsH(D) in baths of H{sub 2}(D{sub 2}) with simultaneous time- and quantum state-resolution. Modal temperatures of vibration, rotation, and translation for CsH(D) were obtained and presented as a function of pump-probe delay time. Here the data from this study are used as a test of the accuracy of the computational method, and in addition, the consequent changes in bath gas modal temperatures, not obtainable in the experiment, are predicted. Despite large discrepancies between initial CsH(D) vibrational states in the experiment and those available using the computational model, the quality of agreement is sufficient to conclude that the model’s predictions constitute at least a very good representation of the overall equilibration that, for some measurements, is very accurate.

Spatially-resolved studies of charge-density-wave phase slip and dynamics in NbSe3

International Nuclear Information System (INIS)

Lemay, S.G.; Adelman, T.L.; Zaitsev-Zotov, S.V.; Thorne, R.E.

1999-01-01

We review our spatially and temporally resolved studies of charge-density-wave (CDW) phase slip and dynamics in NbSe 3 . Measurements of the steady-state CDW current, phase slip and strain profiles and their transient evolutions in response to a change in current direction provide a detailed picture of the interplay between elastic deformations and plasticity in this material. (orig.)

Minimum resolvable power contrast model

Science.gov (United States)

Qian, Shuai; Wang, Xia; Zhou, Jingjing

2018-01-01

Signal-to-noise ratio and MTF are important indexs to evaluate the performance of optical systems. However,whether they are used alone or joint assessment cannot intuitively describe the overall performance of the system. Therefore, an index is proposed to reflect the comprehensive system performance-Minimum Resolvable Radiation Performance Contrast (MRP) model. MRP is an evaluation model without human eyes. It starts from the radiance of the target and the background, transforms the target and background into the equivalent strips,and considers attenuation of the atmosphere, the optical imaging system, and the detector. Combining with the signal-to-noise ratio and the MTF, the Minimum Resolvable Radiation Performance Contrast is obtained. Finally the detection probability model of MRP is given.

Steady-state and time-resolved spectroscopic investigations on intramolecular electron transfer processes within a synthesized methoxynaphthalene dyad by using a nematic liquid crystal medium

International Nuclear Information System (INIS)

Bardhan, Munmun; Mandal, Paulami; De, Asish; Kumar De, Avijit; Chowdhury, Joydeep; Ganguly, Tapan

2010-01-01

UV-vis, steady state and time-resolved spectroscopic investigations were made on photoinduced charge separation and thermal charge recombination processes involved within a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxynaphthalene (MNT) and the acceptor p-choloroacetophenone (PCA) moieties are connected by a short unsaturated olefinic bond. The measurements were made within the pseudo-ordered domain (just above nematic-isotropic (N-I) phase transition temperature, >308 K) of a nematic liquid crystal, 4-(n-pentyl)-4'-cyanobiphenyl (5CB). Results observed are compared with those obtained from the similar measurements in isotropic media. The charge separation and recombination rates remain more-or-less unchanged within the experimental error irrespective of the polarity of the environment, whether in pseudo-ordered domain (ε S ∼10.5) of a nematic liquid crystal 5CB or in highly polar isotropic medium ACN (ε S ∼37.5). The structural rigidity of the dyad MNCA having stable elongated form both in the ground as well as in the photoexcited states seems to be the reason for this unique behavior of solvent insensitivity. The theoretical predictions done by ab initio method density functional theory (DFT) with B3LYP/6-311 G (d, p) basis function correlate well with experimental observations of formations of only one stable elongated (E-type) conformer both in the ground and electronic excited state.

Steady-state and time-resolved spectroscopic investigations on intramolecular electron transfer processes within a synthesized methoxynaphthalene dyad by using a nematic liquid crystal medium

Energy Technology Data Exchange (ETDEWEB)

Bardhan, Munmun; Mandal, Paulami; De, Asish; Kumar De, Avijit [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India); Chowdhury, Joydeep [Sammilani Mahavidyalaya Baghajatin Station, West Bengal (India); Ganguly, Tapan, E-mail: sptg@mahendra.iacs.res.i [Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, West Bengal (India)

2010-06-15

UV-vis, steady state and time-resolved spectroscopic investigations were made on photoinduced charge separation and thermal charge recombination processes involved within a novel synthesized dyad, 1-(4-chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA) where the donor 1-methoxynaphthalene (MNT) and the acceptor p-choloroacetophenone (PCA) moieties are connected by a short unsaturated olefinic bond. The measurements were made within the pseudo-ordered domain (just above nematic-isotropic (N-I) phase transition temperature, >308 K) of a nematic liquid crystal, 4-(n-pentyl)-4'-cyanobiphenyl (5CB). Results observed are compared with those obtained from the similar measurements in isotropic media. The charge separation and recombination rates remain more-or-less unchanged within the experimental error irrespective of the polarity of the environment, whether in pseudo-ordered domain (epsilon{sub S}approx10.5) of a nematic liquid crystal 5CB or in highly polar isotropic medium ACN (epsilon{sub S}approx37.5). The structural rigidity of the dyad MNCA having stable elongated form both in the ground as well as in the photoexcited states seems to be the reason for this unique behavior of solvent insensitivity. The theoretical predictions done by ab initio method density functional theory (DFT) with B3LYP/6-311 G (d, p) basis function correlate well with experimental observations of formations of only one stable elongated (E-type) conformer both in the ground and electronic excited state.

The Resolved Stellar Populations Early Release Science Program

Science.gov (United States)

Weisz, Daniel; Anderson, J.; Boyer, M.; Cole, A.; Dolphin, A.; Geha, M.; Kalirai, J.; Kallivayalil, N.; McQuinn, K.; Sandstrom, K.; Williams, B.

2017-11-01

We propose to obtain deep multi-band NIRCam and NIRISS imaging of three resolved stellar systems within 1 Mpc (NOI 104). We will use this broad science program to optimize observational setups and to develop data reduction techniques that will be common to JWST studies of resolved stellar populations. We will combine our expertise in HST resolved star studies with these observations to design, test, and release point spread function (PSF) fitting software specific to JWST. PSF photometry is at the heart of resolved stellar populations studies, but is not part of the standard JWST reduction pipeline. Our program will establish JWST-optimized methodologies in six scientific areas: star formation histories, measurement of the sub-Solar mass stellar IMF, extinction maps, evolved stars, proper motions, and globular clusters, all of which will be common pursuits for JWST in the local Universe. Our observations of globular cluster M92, ultra-faint dwarf Draco II, and star-forming dwarf WLM, will be of high archival value for other science such as calibrating stellar evolution models, measuring properties of variable stars, and searching for metal-poor stars. We will release the results of our program, including PSF fitting software, matched HST and JWST catalogs, clear documentation, and step-by-step tutorials (e.g., Jupyter notebooks) for data reduction and science application, to the community prior to the Cycle 2 Call for Proposals. We will host a workshop to help community members plan their Cycle 2 observations of resolved stars. Our program will provide blueprints for the community to efficiently reduce and analyze JWST observations of resolved stellar populations.

An experimentalist's guide to the matrix element in angle resolved photoemission

International Nuclear Information System (INIS)

Moser, Simon

2017-01-01

Highlights: • An introduction to the art of angle resolved photoemission is presented. • Matrix element effects are described by a nearly free electron final state model. • ARPES spectral weight of a Bloch band can be calculated from the Fourier transform of its Wannier orbital. • Experimental handedness and improper polarization introduce dichroism. • Instructive showcases from modern ARPES are discussed in detail. - Abstract: Angle resolved photoemission spectroscopy (ARPES) is commonly known as a powerful probe of the one-electron removal spectral function in ordered solid state. With increasing efficiency of light sources and spectrometers, experiments over a wide range of emission angles become more and more common. Consequently, the angular variation of ARPES spectral weight – often times termed “matrix element effect” – enters as an additional source of information. In this tutorial, we develop a simple but instructive free electron final state approach based on the three-step model to describe the intensity distribution in ARPES. We find a compact expression showing that the ARPES spectral weight of a given Bloch band is essentially determined by the momentum distribution (the Fourier transform) of its associated Wannier orbital – times a polarization dependent pre-factor. While the former is giving direct information on the symmetry and shape of the electronic wave function, the latter can give rise to surprising geometric effects. We discuss a variety of modern and instructive experimental showcases for which this simplistic formalism works astonishingly well and discuss the limits of this approach.

An experimentalist's guide to the matrix element in angle resolved photoemission

Energy Technology Data Exchange (ETDEWEB)

Moser, Simon, E-mail: skmoser@lbl.gov [Advanced Light Source (ALS), Berkeley, CA 94720 (United States); Institute of Physics (IPHYS), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland)

2017-01-15

Highlights: • An introduction to the art of angle resolved photoemission is presented. • Matrix element effects are described by a nearly free electron final state model. • ARPES spectral weight of a Bloch band can be calculated from the Fourier transform of its Wannier orbital. • Experimental handedness and improper polarization introduce dichroism. • Instructive showcases from modern ARPES are discussed in detail. - Abstract: Angle resolved photoemission spectroscopy (ARPES) is commonly known as a powerful probe of the one-electron removal spectral function in ordered solid state. With increasing efficiency of light sources and spectrometers, experiments over a wide range of emission angles become more and more common. Consequently, the angular variation of ARPES spectral weight – often times termed “matrix element effect” – enters as an additional source of information. In this tutorial, we develop a simple but instructive free electron final state approach based on the three-step model to describe the intensity distribution in ARPES. We find a compact expression showing that the ARPES spectral weight of a given Bloch band is essentially determined by the momentum distribution (the Fourier transform) of its associated Wannier orbital – times a polarization dependent pre-factor. While the former is giving direct information on the symmetry and shape of the electronic wave function, the latter can give rise to surprising geometric effects. We discuss a variety of modern and instructive experimental showcases for which this simplistic formalism works astonishingly well and discuss the limits of this approach.

340 nm pulsed UV LED system for europium-based time-resolved fluorescence detection of immunoassays

DEFF Research Database (Denmark)

Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter

2016-01-01

We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng....../L in immunoassay. The signal-to-noise ratio was comparable to state-of-the-art Xenon flash lamp based unit with equal excitation energy and without overdriving the LED. We performed a comparative study of the flash lamp and the LED based system and discussed temporal, spatial, and spectral features of the LED...... excitation for time-resolved fluorimetry. Optimization of the suggested key parameters of the LED promises significant increase of the signal-to-noise ratio and hence of the sensitivity of immunoassay systems....

340 nm pulsed UV LED system for europium-based time-resolved fluorescence detection of immunoassays.

Science.gov (United States)

Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter; Petersen, Paul Michael; Pedersen, Christian

2016-09-19

We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng/L in immunoassay. The signal-to-noise ratio was comparable to state-of-the-art Xenon flash lamp based unit with equal excitation energy and without overdriving the LED. We performed a comparative study of the flash lamp and the LED based system and discussed temporal, spatial, and spectral features of the LED excitation for time-resolved fluorimetry. Optimization of the suggested key parameters of the LED promises significant increase of the signal-to-noise ratio and hence of the sensitivity of immunoassay systems.

Spatially Resolved Gas Temperature Measurements in an Atmospheric Pressure DC Glow Microdischarge with Raman Scattering

Science.gov (United States)

Belostotskiy, S.; Wang, Q.; Donnelly, V.; Economou, D.; Sadeghi, N.

2006-10-01

Spatially resolved rotational Raman spectroscopy of ground state nitrogen N2(X^1σg^+) was used to measure the gas temperature (Tg) in a nitrogen dc glow microdischarge (gap between electrodes d˜500 μm). An original backscattering, confocal optical system was developed for collecting Raman spectra. Stray laser light and Raleigh scattering were blocked by using a triple grating monochromator and spatial filters, designed specifically for these experiments. The optical system provided a spatial resolution of electrodes, Tg increased linearly with jd, reaching 500 K at 1000 mA/cm^2 jd for a pressure of 720 Torr. Spatially resolved gas temperature measurements will also be presented and discussed in combination with a mathematical model for gas heating in the microplasma. This work is supported by DoE/NSF.

Rapid high-resolution spin- and angle-resolved photoemission spectroscopy with pulsed laser source and time-of-flight spectrometer

Science.gov (United States)

Gotlieb, K.; Hussain, Z.; Bostwick, A.; Lanzara, A.; Jozwiak, C.

2013-09-01

A high-efficiency spin- and angle-resolved photoemission spectroscopy (spin-ARPES) spectrometer is coupled with a laboratory-based laser for rapid high-resolution measurements. The spectrometer combines time-of-flight (TOF) energy measurements with low-energy exchange scattering spin polarimetry for high detection efficiencies. Samples are irradiated with fourth harmonic photons generated from a cavity-dumped Ti:sapphire laser that provides high photon flux in a narrow bandwidth, with a pulse timing structure ideally matched to the needs of the TOF spectrometer. The overall efficiency of the combined system results in near-EF spin-resolved ARPES measurements with an unprecedented combination of energy resolution and acquisition speed. This allows high-resolution spin measurements with a large number of data points spanning multiple dimensions of interest (energy, momentum, photon polarization, etc.) and thus enables experiments not otherwise possible. The system is demonstrated with spin-resolved energy and momentum mapping of the L-gap Au(111) surface states, a prototypical Rashba system. The successful integration of the spectrometer with the pulsed laser system demonstrates its potential for simultaneous spin- and time-resolved ARPES with pump-probe based measurements.

State-to-state dynamics of molecular energy transfer

Energy Technology Data Exchange (ETDEWEB)

Gentry, W.R.; Giese, C.F. [Univ. of Minnesota, Minneapolis (United States)

1993-12-01

The goal of this research program is to elucidate the elementary dynamical mechanisms of vibrational and rotational energy transfer between molecules, at a quantum-state resolved level of detail. Molecular beam techniques are used to isolate individual molecular collisions, and to control the kinetic energy of collision. Lasers are used both to prepare specific quantum states prior to collision by stimulated-emission pumping (SEP), and to measure the distribution of quantum states in the collision products by laser-induced fluorescence (LIF). The results are interpreted in terms of dynamical models, which may be cast in a classical, semiclassical or quantum mechanical framework, as appropriate.

Mapping the Decision-Making Process for Adjuvant Endocrine Therapy for Breast Cancer: The Role of Decisional Resolve.

Science.gov (United States)

Beryl, Louise L; Rendle, Katharine A S; Halley, Meghan C; Gillespie, Katherine A; May, Suepattra G; Glover, Jennifer; Yu, Peter; Chattopadhyay, Runi; Frosch, Dominick L

2017-01-01

Studies show adjuvant endocrine therapy increases survival and decreases risk of breast cancer recurrence for hormone receptor-positive tumors. Yet studies also suggest that adherence rates among women taking this therapy may be as low as 50% owing largely to adverse side effects. Despite these rates, research on longitudinal patient decision making regarding this therapy is scant. We sought to map the decision-making process for women considering and initiating adjuvant endocrine therapy, paying particular attention to patterns of uncertainty and decisional change over time. A longitudinal series of semistructured interviews conducted at a multispecialty health care organization in Northern California with 35 newly diagnosed patients eligible for adjuvant endocrine therapy were analyzed. Analysis led to the identification and indexing of 3 new decision-making constructs-decisional phase, decisional direction, and decisional resolve-which were then organized using a visual matrix and examined for patterns characterizing the decision-making process. Our data reveal that most patients do not make a single, discrete decision to take or not take hormone therapy but rather traverse multiple decisional states, characterized by 1) phase, 2) direction, and 3) strength of resolve. Our analysis tracks these decisional states longitudinally using a grayscale-coded matrix. Our data show that decisional resolve wavers not just when considering therapy, as the existing concept of decisional conflict suggests, but even after initiating it, which may signal future decisions to forgo therapy. Adjuvant endocrine therapy, like other chronic care decisions, has a longer decision-making process and implementation period. Thus, theoretical, empirical, and clinical approaches should consider further exploring the new concept and measurement of decisional resolve, as it may help to improve subsequent medication adherence. © The Author(s) 2016.

Angle-resolved photoemission in high Tc cuprates from theoretical viewpoints

International Nuclear Information System (INIS)

Tohyama, T.; Maekawa, S.

2000-01-01

The angle-resolved photoemission (ARPES) technique has been developed rapidly over the last decade, accompanied by the improvement of energy and momentum resolutions. This technique has been established as the most powerful tool to investigate the high T c cuprate superconductors. We review recent ARPES data on the cuprates from a theoretical point of view, with emphasis on the systematic evolution of the spectral weight near the momentum (π, 0) from insulator to overdoped systems. The effects of charge stripes on the ARPES spectra are also reviewed. Some recent experimental and theoretical efforts to understand the superconducting state and the pseudogap phenomenon are discussed. (author)

Gauge invariance in the theoretical description of time-resolved angle-resolved pump/probe photoemission spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Freericks, J. K.; Krishnamurthy, H. R.; Sentef, M. A.; Devereaux, T. P.

2015-10-01

Nonequilibrium calculations in the presence of an electric field are usually performed in a gauge, and need to be transformed to reveal the gauge-invariant observables. In this work, we discuss the issue of gauge invariance in the context of time-resolved angle-resolved pump/probe photoemission. If the probe is applied while the pump is still on, one must ensure that the calculations of the observed photocurrent are gauge invariant. We also discuss the requirement of the photoemission signal to be positive and the relationship of this constraint to gauge invariance. We end by discussing some technical details related to the perturbative derivation of the photoemission spectra, which involve processes where the pump pulse photoexcites electrons due to nonequilibrium effects.

The TimBel synchronization board for time resolved experiments at synchrotron SOLEIL

International Nuclear Information System (INIS)

Ricaud, J.P.; Betinelli-Deck, P.; Bisou, J.; Elattaoui, X.; Laulhe, C.; Monteiro, P.; Nadolski, L.S.; Renaud, G.; Ravy, S.; Silly, M.; Sirotti, F.

2012-01-01

Time resolved experiments are one of the major services that synchrotrons can provide to scientists. The short, high frequency and regular flashes of synchrotron light are a fantastic tool to study the evolution of phenomena over time. To carry out time resolved experiments, beamlines need to synchronize their devices with these flashes of light with a jitter shorter than the pulse duration. For that purpose, Synchrotron SOLEIL has developed the TimBeL (Timing Beamlines) board fully interfaced to TANGO framework. The TimBeL system is a compact PCI board. It is made of a mother with one daughter board. All functions are performed inside a FPGA (Field Programmable Gate Array) implemented on the mother board. A PLX Technology chip is used to communicate with the compact PCI crate. To enable experiments to remain always synchronous with the same bunch of electrons, the storage ring clock (CLK-SR) and the radio frequency clock (CLK-RF) are provided by the machine to beamlines. These clocks are used inside the FPGA as main clocks for state machines. Because the jitter is too large on the FPGA outputs, a daughter board with a jitter cleaner has been added to the system. This board also provides delay lines for compensating time offsets by 10 ps steps. This paper presents the main features required by time resolved experiments and how we achieved our goals with the TimBeL board

Particle tracking during Ostwald ripening using time-resolved laboratory X-ray microtomography

Energy Technology Data Exchange (ETDEWEB)

Werz, T., E-mail: thomas.werz@uni-ulm.de [Ulm University, Institute of Micro and Nanomaterials, Albert-Einstein-Allee 47, 89081 (Germany); Baumann, M. [Ulm University, Institute of Micro and Nanomaterials, Albert-Einstein-Allee 47, 89081 (Germany); Wolfram, U. [Ulm University, Institute of Orthopaedic Research and Biomechanics, Helmholtzstrasse 14, 89081 (Germany); Krill, C.E. [Ulm University, Institute of Micro and Nanomaterials, Albert-Einstein-Allee 47, 89081 (Germany)

2014-04-01

Laboratory X-ray microtomography is investigated as a method for obtaining time-resolved images of microstructural coarsening of the semisolid state of Al–5 wt.% Cu samples during Ostwald ripening. Owing to the 3D imaging capability of tomography, this technique uniquely provides access to the growth rates of individual particles, thereby not only allowing a statistical characterization of coarsening—as has long been possible by conventional metallography—but also enabling quantification of the influence of local environment on particle boundary migration. The latter information is crucial to understanding growth kinetics during Ostwald ripening at high volume fractions of the coarsening phase. Automated image processing and segmentation routines were developed to close gaps in the network of particle boundaries and to track individual particles from one annealing step to the next. The particle tracking success rate places an upper bound of only a few percent on the likelihood of segmentation errors for any given particle. The accuracy of particle size trajectories extracted from the time-resolved tomographic reconstructions is correspondingly high. Statistically averaged coarsening data and individual particle growth rates are in excellent agreement with the results of prior experimental studies and with computer simulations of Ostwald ripening. - Highlights: • Ostwald ripening in Al–5 wt.% Cu measured by laboratory X-ray microtomography • Time-resolved measurement of individual particle growth • Automated segmentation routines developed to close gaps in particle boundary network • Particle growth/shrinkage rates deviate from LSW model prediction.

Study on sociological approach to resolve maintenance related social problems

International Nuclear Information System (INIS)

Aoki, Takayuki

2007-01-01

This study proposes a sociological approach to resolve maintenance related social problems. As a result of consideration, the followings were found. (1) In general, solutions to some kinds of questions can be deduced from basic laws using some theories or methodologies in the field of the natural science or engineering. The approach to resolve maintenance related social problems is similar to the approach in the natural science or engineering. (2) The points of view based on fundamental human rights, market principles and community principles, and so on, are very important in resolving maintenance related social problems and can be placed as theories or tools for resolution. (3) If such theories or tools for resolving maintenance related social problems as described above are systematically prepared, it is estimated that it becomes very much easier to resolve maintenance related social problems. (author)

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

International Nuclear Information System (INIS)

Vanko, Gyorgy; Bordage, Amelie; Papai, Matyas; Haldrup, Kristoffer; March, Anne Marie; Galler, Andreas; Assefa, Tadesse; Cabaret, Delphine; Juhin, Amelie; Driel, Tim B. van; Gallo, Erik; Rovezzi, Mauro; Nemeth, Zoltan; Rozsalyi, Emese; Rozgonyi, Tamas; Uhlig, Jens; Gawelda, Wojciech

2015-01-01

Theoretical predictions show that depending on the populations of the Fe 3d xy , 3d xz , and 3d yz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy) 2 ] 2+ . The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy) 2 ] 2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy) 2 ] 2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe-ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)-high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations

Spin-resolved magnetic studies of focused ion beam etched nano-sized magnetic structures

International Nuclear Information System (INIS)

Li Jian; Rau, Carl

2005-01-01

Scanning ion microscopy with polarization analysis (SIMPA) is used to study the spin-resolved surface magnetic structure of nano-sized magnetic systems. SIMPA is utilized for in situ topographic and spin-resolved magnetic domain imaging as well as for focused ion beam (FIB) etching of desired structures in magnetic or non-magnetic systems. Ultra-thin Co films are deposited on surfaces of Si(1 0 0) substrates, and ultra-thin, tri-layered, bct Fe(1 0 0)/Mn/bct Fe(1 0 0) wedged magnetic structures are deposited on fcc Pd(1 0 0) substrates. SIMPA experiments clearly show that ion-induced electrons emitted from magnetic surfaces exhibit non-zero electron spin polarization (ESP), whereas electrons emitted from non-magnetic surfaces such as Si and Pd exhibit zero ESP, which can be used to calibrate sputtering rates in situ. We report on new, spin-resolved magnetic microstructures, such as magnetic 'C' states and magnetic vortices, found at surfaces of FIB patterned magnetic elements. It is found that FIB milling has a negligible effect on surface magnetic domain and domain wall structures. It is demonstrated that SIMPA can evolve into an important and efficient tool to study magnetic domain, domain wall and other structures as well as to perform magnetic depth profiling of magnetic nano-systems to be used in ultra-high density magnetic recording and in magnetic sensors

RESOLVE's Field Demonstration on Mauna Kea, Hawaii 2010

Science.gov (United States)

Captain, Janine; Quinn, Jacqueline; Moss, Thomas; Weis, Kyle

2010-01-01

In cooperation with the Canadian Space Agency, and the Northern Centre for Advanced Technology, Inc., NASA has undertaken the In-Situ Resource Utilization (ISRU) project called RESOLVE (Regolith and Environment Science & Oxygen and Lunar Volatile Extraction). This project is an Earth-based lunar precursor demonstration of a system that could be sent to explore permanently shadowed polar lunar craters, where it would drill into regolith, quantify the volatiles that are present, and extract oxygen by hydrogen reduction of iron oxides. The resulting water could be electrolyzed into oxygen to support exploration and hydrogen, which would be recycled through the process. The RESOLVE chemical processing system was mounted on a Canadian Space Agency mobility chasis and successfully demonstrated on Hawaii's Mauna Kea volcano in February 2010. The RESOLVE unit is the initial prototype of a robotic prospecting mission to the Moon. RESOLVE is designed to go to the poles of the Moon to "ground truth" the form and concentration of the hydrogen/water/hydroxyl that has been seen from orbit (M3, Lunar Prospector and LRO) and to test technologies to extract oxygen from the lunar regolith. RESOLVE has the ability to capture a one-meter core sample of lunar regolith and heat it to determine the volatiles that may be released and then demonstrate the production of oxygen from minerals found in the regolith. The RESOLVE project, which is led by KSC, is a multi-center and multi-organizational effort that includes representatives from KSC, JSC, GRC, the Canadian Space Agency, and the Northern Center for Advanced Technology (NORCAT). This paper details the results obtained from four days of lunar analog testing that included gas chromatograph analysis for volatile components, remote control of chemistry and drilling operations via satalite communications, and real-time water quantification using a novel capacitance measurement technique.

Fully resolved simulations of expansion waves propagating into particle beds

Science.gov (United States)

Marjanovic, Goran; Hackl, Jason; Annamalai, Subramanian; Jackson, Thomas; Balachandar, S.

2017-11-01

There is a tremendous amount of research that has been done on compression waves and shock waves moving over particles but very little concerning expansion waves. Using 3-D direct numerical simulations, this study will explore expansion waves propagating into fully resolved particle beds of varying volume fractions and geometric arrangements. The objectives of these simulations are as follows: 1) To fully resolve all (1-way coupled) forces on the particles in a time varying flow and 2) to verify state-of-the-art drag models for such complex flows. We will explore a range of volume fractions, from very low ones that are similar to single particle flows, to higher ones where nozzling effects are observed between neighboring particles. Further, we will explore two geometric arrangements: body centered cubic and face centered cubic. We will quantify the effects that volume fraction and geometric arrangement plays on the drag forces and flow fields experienced by the particles. These results will then be compared to theoretical predictions from a model based on the generalized Faxen's theorem. This work was supported in part by the U.S. Department of Energy under the Predictive Science Academic Alliance Program, under Contract No. DE-NA0002378.

An x-ray detector for time-resolved studies

International Nuclear Information System (INIS)

Rodricks, B.; Brizard, C.; Clarke, R.; Lowe, W.

1992-01-01

The development of ultrahigh-brightness x-ray sources makes time-resolved x-ray studies more and more feasible. Improvements in x-ray optics components are also critical for obtaining the appropriate beam for a particular type of experiment. Moreover, fast parallel detectors will be essential in order to exploit the combination of high intensity x-ray sources and novel optics for time-resolved experiments. A CCD detector with a time resolution of microseconds has been developed at the Advanced Photon Source (APS). This detector is fully programmable using CAMAC electronics and a Micro Vax computer. The techniques of time-resolved x-ray studies, which include scattering, microradiography, microtomography, stroboscopy, etc., can be applied to a range of phenomena (including rapid thermal annealing, surface ordering, crystallization, and the kinetics of phase transition) in order to understand these time-dependent microscopic processes. Some of these applications will be illustrated by recent results performed at synchrotrons. New powerful x-ray sources now under construction offer the opportunity to apply innovative approaches in time-resolved work

The social ecology of resolving family conflict among West African immigrants in New York: a grounded theory approach.

Science.gov (United States)

Rasmussen, Andrew; Chu, Tracy; Akinsulure-Smith, Adeyinka M; Keatley, Eva

2013-09-01

The current study employs a grounded theory approach to examine West African immigrants' resolution of parent-child conflict and intimate partner conflict. Data from 59 participants present an interactive social ecological framework, where a lack of resolution at one level results in attempts to resolve problems at higher levels. Four levels are identified within West African immigrants' problem solving ecology, each with specific actors in positions of authority: individual/dyadic (parents and spouses), extended family (which includes distant relatives and relatives living in home countries), community leadership (non-family elders and religious leaders), and state authorities. From participants' descriptions of family challenges emerged a picture of a social ecology in flux, with traditional, socially conservative modes of resolving family conflict transposed across migration into the more liberal and state-oriented familial context of the United States. This transposition results in a loss spiral for the traditional social ecology, differentially affecting individual actors within families. Implications for helping professionals working with new immigrant communities include identifying variability in openness to adapting structures that are not working well (e.g., patriarchal protection of abusive husbands) and supporting structures known to be associated with well being (e.g., collective monitoring of youth).

Resolved, expanding jets in the Galactic black hole candidate XTE J1908+094

Science.gov (United States)

Rushton, A. P.; Miller-Jones, J. C. A.; Curran, P. A.; Sivakoff, G. R.; Rupen, M. P.; Paragi, Z.; Spencer, R. E.; Yang, J.; Altamirano, D.; Belloni, T.; Fender, R. P.; Krimm, H. A.; Maitra, D.; Migliari, S.; Russell, D. M.; Russell, T. D.; Soria, R.; Tudose, V.

2017-07-01

Black hole X-ray binaries undergo occasional outbursts caused by changing inner accretion flows. Here we report high angular resolution radio observations of the 2013 outburst of the black hole candidate X-ray binary system XTE J1908+094, using data from the Very Long Baseline Array and European VLBI Network. We show that following a hard-to-soft state transition, we detect moving jet knots that appear asymmetric in morphology and brightness, and expand to become laterally resolved as they move away from the core, along an axis aligned approximately -11° east of north. We initially see only the southern component, whose evolution gives rise to a 15-mJy radio flare and generates the observed radio polarization. This fades and becomes resolved out after 4 days, after which a second component appears to the north, moving in the opposite direction. From the timing of the appearance of the knots relative to the X-ray state transition, a 90° swing of the inferred magnetic field orientation, the asymmetric appearance of the knots, their complex and evolving morphology, and their low speeds, we interpret the knots as working surfaces where the jets impact the surrounding medium. This would imply a substantially denser environment surrounding XTE J1908+094 than has been inferred to exist around the microquasar sources GRS 1915+105 and GRO J1655-40.

Excited state kinetics of anthracene-bridge-aniline intramolecular exciplexes

DEFF Research Database (Denmark)

Thyrhaug, Erling; Hammershøj, Peter; Kjær, Kasper Skov

2014-01-01

excited anthracene state (LE) and an excited state complex (exciplex, EP) in non-polar solvents. The kinetics of the excited state processes were established in decalin from the time-resolved emission, and was shown to be strongly influenced by an electron-transfer state (ET). For quantitative studies...

Time-resolved photoluminescence of SiOx encapsulated Si

Science.gov (United States)

Kalem, Seref; Hannas, Amal; Österman, Tomas; Sundström, Villy

Silicon and its oxide SiOx offer a number of exciting electrical and optical properties originating from defects and size reduction enabling engineering new electronic devices including resistive switching memories. Here we present the results of photoluminescence dynamics relevant to defects and quantum confinement effects. Time-resolved luminescence at room temperature exhibits an ultrafast decay component of less than 10 ps at around 480 nm and a slower component of around 60 ps as measured by streak camera. Red shift at the initial stages of the blue luminescence decay confirms the presence of a charge transfer to long lived states. Time-correlated single photon counting measurements revealed a life-time of about 5 ns for these states. The same quantum structures emit in near infrared close to optical communication wavelengths. Nature of the emission is described and modeling is provided for the luminescence dynamics. The electrical characteristics of metal-oxide-semiconductor devices were correlated with the optical and vibrational measurement results in order to have better insight into the switching mechanisms in such resistive devices as possible next generation RAM memory elements. ``This work was supported by ENIAC Joint Undertaking and Laser-Lab Europe''.

Quantum information processing with mesoscopic photonic states

DEFF Research Database (Denmark)

Madsen, Lars Skovgaard

2012-01-01

photon numbers and the states where one of Stokes parameters is highly excited. To describe the polarization of these state we introduce several new polarization measures which take into account the covariance of the polarization and resolve the polarization manifolds. We experimentally demonstrate...

Theoretical resolving power of a radiofrequency mass spectrometer

International Nuclear Information System (INIS)

Coc, A.; Le Gac, R.; Saint Simon, M. de; Thibault, C.; Touchard, F.

1988-01-01

Radiofrequency mass spectrometers of L.G. Smith's type can reach a resolving power of 10 6 -10 7 and a precision of 10 -9 -10 -10 . The resolving power, shape of peaks and limitations are described. As an example, the spectrometer to be used in an experiment aimed at measuring the anti p/p mass ratio is considered. (orig.)

An analytic approach to resolving problems in medical ethics.

Science.gov (United States)

Candee, D; Puka, B

1984-01-01

Education in ethics among practising professionals should provide a systematic procedure for resolving moral problems. A method for such decision-making is outlined using the two classical orientations in moral philosophy, teleology and deontology. Teleological views such as utilitarianism resolve moral dilemmas by calculating the excess of good over harm expected to be produced by each feasible alternative for action. The deontological view focuses on rights, duties, and principles of justice. Both methods are used to resolve the 1971 Johns Hopkins case of a baby born with Down's syndrome and duodenal atresia. PMID:6234395

An analytic approach to resolving problems in medical ethics.

Science.gov (United States)

Candee, D; Puka, B

1984-06-01

Education in ethics among practising professionals should provide a systematic procedure for resolving moral problems. A method for such decision-making is outlined using the two classical orientations in moral philosophy, teleology and deontology. Teleological views such as utilitarianism resolve moral dilemmas by calculating the excess of good over harm expected to be produced by each feasible alternative for action. The deontological view focuses on rights, duties, and principles of justice. Both methods are used to resolve the 1971 Johns Hopkins case of a baby born with Down's syndrome and duodenal atresia.

Time-resolved X-ray transmission microscopy on magnetic microstructures

International Nuclear Information System (INIS)

Puzic, Aleksandar

2007-01-01

Three excitation schemes were designed for stroboscopic imaging of magnetization dynamics with time-resolved magnetic transmission X-ray microscopy (TR-MTXM). These techniques were implemented into two types of X-ray microscopes, namely the imaging transmission X-ray microscope (ITXM) and the scanning transmission X-ray microscope (STXM), both installed at the electron storage ring of the Advanced Light Source in Berkeley, USA. Circular diffraction gratings (Fresnel zone plates) used in both microscopes as focusing and imaging elements presently allow for lateral resolution down to 30 nm. Magnetic imaging is performed by using the X-ray magnetic circular dichroism (XMCD) as element specific contrast mechanism. The developed methods have been successfully applied to the experimental investigation of magnetization dynamics in ferromagnetic microstructures. A temporal resolution well below 100 ps was achieved. A conventional pump-probe technique was implemented first. The dynamic response of the magnetization excited by a broadband pulsed magnetic field was imaged spatially resolved using focused X-ray flashes. As a complementary method, the spatially resolved ferromagnetic resonance (SR-FMR) technique was developed for experimental study of magnetization dynamics in the frequency domain. As a third excitation mode, the burst excitation was implemented. The performance and efficiency of the developed methods have been demonstrated by imaging the local magnetization dynamics in laterally patterned ferromagnetic thin-film elements and three-layer stacks. The existence of multiple eigenmodes in the excitation spectra of ferromagnetic microstructures has been verified by using the pump-probe technique. Magnetostatic spin waves were selectively excited and detected with a time resolution of 50 ps using the SR-FMR technique. Thorough analysis of 20 in most cases independently prepared samples has verified that vortices which exhibit a low-amplitude switching of their core

Improvements in brain activation detection using time-resolved diffuse optical means

Science.gov (United States)

Montcel, Bruno; Chabrier, Renee; Poulet, Patrick

2005-08-01

An experimental method based on time-resolved absorbance difference is described. The absorbance difference is calculated over each temporal step of the optical signal with the time-resolved Beer-Lambert law. Finite element simulations show that each step corresponds to a different scanned zone and that cerebral contribution increases with the arrival time of photons. Experiments are conducted at 690 and 830 nm with a time-resolved system consisting of picosecond laser diodes, micro-channel plate photo-multiplier tube and photon counting modules. The hemodynamic response to a short finger tapping stimulus is measured over the motor cortex. Time-resolved absorbance difference maps show that variations in the optical signals are not localized in superficial regions of the head, which testify for their cerebral origin. Furthermore improvements in the detection of cerebral activation is achieved through the increase of variations in absorbance by a factor of almost 5 for time-resolved measurements as compared to non-time-resolved measurements.

Time-resolved fluorometry of the aromatic amino acids

International Nuclear Information System (INIS)

Laws, W.R.; Ross, J.B.A.; Katsoyannis, P.G.; Wyssbrod, H.R.

1988-01-01

The aromatic amino acids tryptophan, tyrosine, and phenylalanine are the chromophores that produce the intrinsic fluorescence of proteins. It has been a long-desired goal to be able to use the fluorescence of these amino acids to help understand protein dynamics, structure, and function. Considerable information about proteins in solution has come from steady-state, or time-averaged, fluorescence measurements, especially from the fluorescence of tryptophan. For a protein to be characterized more extensively, however, the time dependence of the intrinsic fluorescence must also be explained. Unfortunately, complex fluorescence decay kinetics have been observed not only for proteins having just a single aromatic amino acid, but also for simple analogues of these amino acids; the cause of these complex decays is not fully understood. Considerable effort must still be made to resolve the mechanisms causing the complex decays

An approach to spin-resolved molecular gas microscopy

Science.gov (United States)

Covey, Jacob P.; De Marco, Luigi; Acevedo, Óscar L.; Rey, Ana Maria; Ye, Jun

2018-04-01

Ultracold polar molecules are an ideal platform for studying many-body physics with long-range dipolar interactions. Experiments in this field have progressed enormously, and several groups are pursuing advanced apparatus for manipulation of molecules with electric fields as well as single-atom-resolved in situ detection. Such detection has become ubiquitous for atoms in optical lattices and tweezer arrays, but has yet to be demonstrated for ultracold polar molecules. Here we present a proposal for the implementation of site-resolved microscopy for polar molecules, and specifically discuss a technique for spin-resolved molecular detection. We use numerical simulation of spin dynamics of lattice-confined polar molecules to show how such a scheme would be of utility in a spin-diffusion experiment.

On marginally resolved objects in optical interferometry

Science.gov (United States)

Lachaume, R.

2003-03-01

With the present and soon-to-be breakthrough of optical interferometry, countless objects shall be within reach of interferometers; yet, most of them are expected to remain only marginally resolved with hectometric baselines. In this paper, we tackle the problem of deriving the properties of a marginally resolved object from its optical visibilities. We show that they depend on the moments of flux distribution of the object: centre, mean angular size, asymmetry, and curtosis. We also point out that the visibility amplitude is a second-order phenomenon, whereas the phase is a combination of a first-order term, giving the location of the photocentre, and a third-order term, more difficult to detect than the visibility amplitude, giving an asymmetry coefficient of the object. We then demonstrate that optical visibilities are not a good model constraint while the object stays marginally resolved, unless observations are carried out at different wavelengths. Finally, we show an application of this formalism to circumstellar discs.

Measurement of fluorophore concentrations and fluorescence quantum yield in tissue-simulating phantoms using three diffusion models of steady-state spatially resolved fluorescence

Energy Technology Data Exchange (ETDEWEB)

Diamond, Kevin R; Farrell, Thomas J; Patterson, Michael S [Department of Medical Physics, Juravinski Cancer Centre and McMaster University, 699 Concession Street, Hamilton, Ontario L8V 5C2 (Canada)

2003-12-21

Steady-state diffusion theory models of fluorescence in tissue have been investigated for recovering fluorophore concentrations and fluorescence quantum yield. Spatially resolved fluorescence, excitation and emission reflectance were calculated by diffusion theory and Monte Carlo simulations, and measured using a multi-fibre probe on tissue-simulating phantoms containing either aluminium phthalocyanine tetrasulfonate (AlPcS{sub 4}), Photofrin or meso-tetra-(4-sulfonatophenyl)-porphine dihydrochloride (TPPS{sub 4}). The accuracy of the fluorophore concentration and fluorescence quantum yield recovered by three different models of spatially resolved fluorescence were compared. The models were based on: (a) weighted difference of the excitation and emission reflectance, (b) fluorescence due to a point excitation source or (c) fluorescence due to a pencil beam excitation source. When literature values for the fluorescence quantum yield were used for each of the fluorophores, the fluorophore absorption coefficient (and hence concentration) at the excitation wavelengthwas recovered with a root-mean-square accuracy of 11.4% using the point source model of fluorescence and 8.0% using the more complicated pencil beam excitation model. The accuracy was calculated over a broad range of optical properties and fluorophore concentrations. The weighted difference of reflectance model performed poorly, with a root-mean-square error in concentration of about 50%. Monte Carlo simulations suggest that there are some situations where the weighted difference of reflectance is as accurate as the other two models, although this was not confirmed experimentally. Estimates of the fluorescence quantum yield in multiple scattering media were also made by determining independently from the fitted absorption spectrum and applying the various diffusion theory models. The fluorescence quantum yields for AlPcS{sub 4} and TPPS{sub 4} were calculated to be 0.59 {+-} 0.03 and 0.121 {+-} 0

Measurement of fluorophore concentrations and fluorescence quantum yield in tissue-simulating phantoms using three diffusion models of steady-state spatially resolved fluorescence

International Nuclear Information System (INIS)

Diamond, Kevin R; Farrell, Thomas J; Patterson, Michael S

2003-01-01

Steady-state diffusion theory models of fluorescence in tissue have been investigated for recovering fluorophore concentrations and fluorescence quantum yield. Spatially resolved fluorescence, excitation and emission reflectance were calculated by diffusion theory and Monte Carlo simulations, and measured using a multi-fibre probe on tissue-simulating phantoms containing either aluminium phthalocyanine tetrasulfonate (AlPcS 4 ), Photofrin or meso-tetra-(4-sulfonatophenyl)-porphine dihydrochloride (TPPS 4 ). The accuracy of the fluorophore concentration and fluorescence quantum yield recovered by three different models of spatially resolved fluorescence were compared. The models were based on: (a) weighted difference of the excitation and emission reflectance, (b) fluorescence due to a point excitation source or (c) fluorescence due to a pencil beam excitation source. When literature values for the fluorescence quantum yield were used for each of the fluorophores, the fluorophore absorption coefficient (and hence concentration) at the excitation wavelengthwas recovered with a root-mean-square accuracy of 11.4% using the point source model of fluorescence and 8.0% using the more complicated pencil beam excitation model. The accuracy was calculated over a broad range of optical properties and fluorophore concentrations. The weighted difference of reflectance model performed poorly, with a root-mean-square error in concentration of about 50%. Monte Carlo simulations suggest that there are some situations where the weighted difference of reflectance is as accurate as the other two models, although this was not confirmed experimentally. Estimates of the fluorescence quantum yield in multiple scattering media were also made by determining independently from the fitted absorption spectrum and applying the various diffusion theory models. The fluorescence quantum yields for AlPcS 4 and TPPS 4 were calculated to be 0.59 ± 0.03 and 0.121 ± 0.001 respectively using the point

[Energy pooling collisions for K(4P) + Cs(5D) in a K-Cs mixture].

Science.gov (United States)

Aihemaiti, Pulati; Dai, Kang; Lu, Xin-hong; Shen, Yi-fan

2005-04-01

The rate coefficients for energy-pooling collisions K(4P) + Cs(5D) --> Cs(6S) + K(4D, 6S) in the K-Cs vapor mixture were measured relative to a known energy-pooling rate coefficient of a homonuclear reaction [i. e., Cs(6P) + Cs(5D) --> Cs(6S) + Cs (7D(J))]. Populations of the Cs(6P, 5D) and K(4P) states were produced by photodissociation of K2 and Cs2 molecules through the use of a dye laser radiation. The resulting fluorescence included the direct components emitted in the decay of the excited states produced by photodissociation and the induced components arising from the collisionally populated states. By combining relative intensities of the components with the effective lifetimes of Cs(6P) and K(4P) states, the rate coefficients (in units of 10(-9) cm3 x s(-1)) for the heteronuclear energy-pooling were found to be 2.6 and 3.6, respectively. The contribution to the rate coefficients from other processes are discussed.

Phased-Resolved Strain Measuremetns in Hydrated Ordinary Portland Cement Using Synchrotron x-Rays (Prop. 2003-033)

International Nuclear Information System (INIS)

Biernacki, Joseph J.; Watkins, Thomas R.; Parnham, C.J.; Hubbard, Camden R.; Bai, J.

2006-01-01

X-ray diffraction methods developed for the determination of residual stress states in crystalline materials have been applied to study residual strains and strains because of mechanical loading of ordinary portland cement paste. Synchrotron X-rays were used to make in situ measurements of interplanar spacings in the calcium hydroxide (CH) phase of hydrated neat portland cement under uniaxial compression. The results indicate that strains on the order of 1/100 000 can be resolved providing an essentially new technique by which to measure the phase-resolved meso-scale mechanical behavior of cement under different loading conditions. Evaluation of these strain data in view of published elastic parameters for CH suggests that the CH carries a large fraction of the applied stress and that plastic interactions with the matrix are notable.

Understanding healthcare professionals' self-efficacy to resolve interprofessional conflict.

Science.gov (United States)

Sexton, Martha; Orchard, Carole

2016-05-01

Conflict within interprofessional healthcare teams, when not effectively resolved, has been linked to detrimental consequences; however, effective conflict resolution has been shown to enhance team performance, increase patient safety, and improve patient outcomes. Alarmingly, knowledge of healthcare professionals' ability to resolve conflict has been limited, largely due to the challenges that arise when researchers attempt to observe a conflict occurring in real time. Research literature has identified three central components that seem to influence healthcare professional's perceived ability to resolve conflict: communication competence, problem-solving ability, and conflict resolution education and training. The purpose of this study was to investigate the impact of communication competence, problem-solving ability, and conflict resolution education and training on healthcare professionals' perceived ability to resolve conflicts. This study employed a cross-sectional survey design. Multiple regression analyses demonstrated that two of the three central components-conflict resolution education and training and communication competence-were found to be statistically significant predictors of healthcare professionals' perceived ability to resolve conflict. Implications include a call to action for clinicians and academicians to recognize the importance of communication competence and conflict resolution education and training as a vital area in interprofessional pre- and post-licensure education and collaborative practice.

Structure-activity relationships of heterogeneous catalysts from time-resolved X-ray absorption spectroscopy

International Nuclear Information System (INIS)

Ressler, T.; Jentoft, R.E.; Wienold, J.; Girgsdies, F.; Neisius, T.; Timpe, O.

2003-01-01

Knowing the composition and the evolution of the bulk structure of a heterogeneous catalyst under working conditions (in situ) is a pre-requisite for understanding structure-activity relationships. X-ray absorption spectroscopy can be employed to study a catalytically active material in situ. In addition to steady-state investigations, the technique permits experiments with a time-resolution in the sub-second range to elucidate the solid-state kinetics of the reactions involved. Combined with mass spectrometry, the evolution of the short-range order structure of a heterogeneous catalyst, the average valence of the constituent metals, and the phase composition can be obtained. Here we present results obtained from time-resolved studies on the reduction of MoO 3 in propene and in propene and oxygen

A high-efficiency spin-resolved photoemission spectrometer combining time-of-flight spectroscopy with exchange-scattering polarimetry

Energy Technology Data Exchange (ETDEWEB)

Jozwiak, Chris M.; Graff, Jeff; Lebedev, Gennadi; Andresen, Nord; Schmid, Andreas; Fedorov, Alexei; El Gabaly, Farid; Wan, Weishi; Lanzara, Alessandra; Hussain, Zahid

2010-04-13

We describe a spin-resolved electron spectrometer capable of uniquely efficient and high energy resolution measurements. Spin analysis is obtained through polarimetry based on low-energy exchange scattering from a ferromagnetic thin-film target. This approach can achieve a similar analyzing power (Sherman function) as state-of-the-art Mott scattering polarimeters, but with as much as 100 times improved efficiency due to increased reflectivity. Performance is further enhanced by integrating the polarimeter into a time-of-flight (TOF) based energy analysis scheme with a precise and flexible electrostatic lens system. The parallel acquisition of a range of electron kinetic energies afforded by the TOF approach results in an order of magnitude (or more) increase in efficiency compared to hemispherical analyzers. The lens system additionally features a 90 degrees bandpass filter, which by removing unwanted parts of the photoelectron distribution allows the TOF technique to be performed at low electron drift energy and high energy resolution within a wide range of experimental parameters. The spectrometer is ideally suited for high-resolution spin- and angle-resolved photoemission spectroscopy (spin-ARPES), and initial results are shown. The TOF approach makes the spectrometer especially ideal for time-resolved spin-ARPES experiments.

Validation of an hourly resolved global aerosol model in answer to solar electricity generation information needs

Directory of Open Access Journals (Sweden)

M. Schroedter-Homscheidt

2013-04-01

Full Text Available Solar energy applications need global aerosol optical depth (AOD information to derive historic surface solar irradiance databases from geostationary meteorological satellites reaching back to the 1980's. This paper validates the MATCH/DLR model originating in the climate community against AERONET ground measurements. Hourly or daily mean AOD model output is evaluated individually for all stations in Europe, Africa and the Middle East – an area highly interesting for solar energy applications being partly dominated by high aerosol loads. Overall, a bias of 0.02 and a root-mean-square error (RMSE of 0.23 are found for daily mean AOD values, while the RMSE increases to 0.28 for hourly mean AOD values. Large differences between various regions and stations are found providing a feedback loop for the aerosol modelling community. The difference in using daily means versus hourly resolved modelling with respect to hourly resolved observations is evaluated. Nowadays state-of-the-art in solar resource assessment relies on monthly turbidity or AOD climatologies while at least hourly resolved irradiance time series are needed by the solar sector. Therefore, the contribution of higher temporally modelled AOD is evaluated.

Method for the deconvolution of incompletely resolved CARS spectra in chemical dynamics experiments

International Nuclear Information System (INIS)

Anda, A.A.; Phillips, D.L.; Valentini, J.J.

1986-01-01

We describe a method for deconvoluting incompletely resolved CARS spectra to obtain quantum state population distributions. No particular form for the rotational and vibrational state distribution is assumed, the population of each quantum state is treated as an independent quantity. This method of analysis differs from previously developed approaches for the deconvolution of CARS spectra, all of which assume that the population distribution is Boltzmann, and thus are limited to the analysis of CARS spectra taken under conditions of thermal equilibrium. The method of analysis reported here has been developed to deconvolute CARS spectra of photofragments and chemical reaction products obtained in chemical dynamics experiments under nonequilibrium conditions. The deconvolution procedure has been incorporated into a computer code. The application of that code to the deconvolution of CARS spectra obtained for samples at thermal equilibrium and not at thermal equilibrium is reported. The method is accurate and computationally efficient

Hole emission from Ge/Si quantum dots studied by time-resolved capacitance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Kapteyn, C.M.A.; Lion, M.; Heitz, R.; Bimberg, D. [Technische Univ. Berlin (Germany). Inst. fuer Festkoerperphysik; Miesner, C.; Asperger, T.; Brunner, K.; Abstreiter, G. [Technische Univ. Muenchen, Garching (Germany). Walter-Schottky-Inst. fuer Physikalische Grundlagen der Halbleiterelektronik

2001-03-01

Emission of holes from self-organized Ge quantum dots (QDs) embedded in Si Schottky diodes is studied by time-resolved capacitance spectroscopy (DLTS). The DLTS signal is rather broad and depends strongly on the filling and detection bias conditions. The observed dependence is interpreted in terms of carrier emission from many-hole states of the QDs. The activation energies obtained from the DLTS measurements are a function of the amount of stored charge and the position of the Fermi level in the QDs. (orig.)

Decay time shortening of fluorescence from donor-acceptor pair proteins using ultrafast time-resolved fluorescence resonance energy transfer spectroscopy

International Nuclear Information System (INIS)

Baba, Motoyoshi; Suzuki, Masayuki; Ganeev, Rashid A.; Kuroda, Hiroto; Ozaki, Tsuneyuki; Hamakubo, Takao; Masuda, Kazuyuki; Hayashi, Masahiro; Sakihama, Toshiko; Kodama, Tatsuhiko; Kozasa, Tohru

2007-01-01

We improved an ultrafast time-resolved fluorescence resonance energy transfer (FRET) spectroscopy system and measured directly the decrease in the fluorescence decay time of the FRET signal, without any entanglement of components in the picosecond time scale from the donor-acceptor protein pairs (such as cameleon protein for calcium ion indicator, and ligand-activated GRIN-Go proteins pair). The drastic decrease in lifetime of the donor protein fluorescence under the FRET condition (e.g. a 47.8% decrease for a GRIN-Go protein pair) proves the deformation dynamics between donor and acceptor fluorescent proteins in an activated state of a mixed donor-acceptor protein pair. This study is the first clear evidence of physical contact of the GRIN-Go proteins pair using time-resolved FRET system. G protein-coupled receptors (GPCRs) are the most important protein family for the recognition of many chemical substances at the cell surface. They are the targets of many drugs. Simultaneously, we were able to observe the time-resolved spectra of luminous proteins at the initial stage under the FRET condition, within 10 ns from excitation. This new FRET system allows us to trace the dynamics of the interaction between proteins at the ligand-induced activated state, molecular structure change and combination or dissociation. It will be a key technology for the development of protein chip technology

Resolving runaway electron distributions in space, time, and energy

Science.gov (United States)

Paz-Soldan, C.; Cooper, C. M.; Aleynikov, P.; Eidietis, N. W.; Lvovskiy, A.; Pace, D. C.; Brennan, D. P.; Hollmann, E. M.; Liu, C.; Moyer, R. A.; Shiraki, D.

2018-05-01

Areas of agreement and disagreement with present-day models of runaway electron (RE) evolution are revealed by measuring MeV-level bremsstrahlung radiation from runaway electrons (REs) with a pinhole camera. Spatially resolved measurements localize the RE beam, reveal energy-dependent RE transport, and can be used to perform full two-dimensional (energy and pitch-angle) inversions of the RE phase-space distribution. Energy-resolved measurements find qualitative agreement with modeling on the role of collisional and synchrotron damping in modifying the RE distribution shape. Measurements are consistent with predictions of phase-space attractors that accumulate REs, with non-monotonic features observed in the distribution. Temporally resolved measurements find qualitative agreement with modeling on the impact of collisional and synchrotron damping in varying the RE growth and decay rate. Anomalous RE loss is observed and found to be largest at low energy. Possible roles for kinetic instability or spatial transport to resolve these anomalies are discussed.

Emerging biomedical applications of time-resolved fluorescence spectroscopy

Science.gov (United States)

Lakowicz, Joseph R.; Szmacinski, Henryk; Koen, Peter A.

1994-07-01

Time-resolved fluorescence spectroscopy is presently regarded as a research tool in biochemistry, biophysics, and chemical physics. Advances in laser technology, the development of long-wavelength probes, and the use of lifetime-based methods are resulting in the rapid migration of time-resolved fluorescence to the clinical chemistry lab, to the patient's bedside, to flow cytometers, to the doctor's office, and even to home health care. Additionally, time-resolved imaging is now a reality in fluorescence microscopy, and will provide chemical imaging of a variety of intracellular analytes and/or cellular phenomena. In this overview paper we attempt to describe some of the opportunities available using chemical sensing based on fluorescence lifetimes, and to predict those applications of lifetime-based sensing which are most likely in the near future.

Time-resolved photoelectron spectrometry of a dephasing process in pyrazine

International Nuclear Information System (INIS)

Pavlov, R.L.; Pavlov, L.I.; Delchev, Ya.I.; Pavlova, S.I.

2001-01-01

The first femtosecond time-resolved photoelectron imaging (PEI) is presented. The method is characterized by photoionization of NO and further applied to ultrafast dephasing in pyrazine. Intermediate case behaviour in radiationless transition is clearly observed in time-resolved photoelectron kinetic energy distribution. Femtosecond PEI is with much improved efficiency than conventional photoelectron spectroscopies. It is anticipated that the unifield approach of time-resolved photoelectron and photoion imaging opens the possibility of observing photon-induced dynamics in real time

WFIRST: Resolving the Milky Way Galaxy

Science.gov (United States)

Kalirai, Jason; Conroy, Charlie; Dressler, Alan; Geha, Marla; Levesque, Emily; Lu, Jessica; Tumlinson, Jason

2018-01-01

WFIRST will yield a transformative impact in measuring and characterizing resolved stellar populations in the Milky Way. The proximity and level of detail that such populations need to be studied at directly map to all three pillars of WFIRST capabilities - sensitivity from a 2.4 meter space based telescope, resolution from 0.1" pixels, and large 0.3 degree field of view from multiple detectors. In this poster, we describe the activities of the WFIRST Science Investigation Team (SIT), "Resolving the Milky Way with WFIRST". Notional programs guiding our analysis include targeting sightlines to establish the first well-resolved large scale maps of the Galactic bulge aand central region, pockets of star formation in the disk, benchmark star clusters, and halo substructure and ultra faint dwarf satellites. As an output of this study, our team is building optimized strategies and tools to maximize stellar population science with WFIRST. This will include: new grids of IR-optimized stellar evolution and synthetic spectroscopic models; pipelines and algorithms for optimal data reduction at the WFIRST sensitivity and pixel scale; wide field simulations of Milky Way environments including new astrometric studies; and strategies and automated algorithms to find substructure and dwarf galaxies in the Milky Way through the WFIRST High Latitude Survey.

Dynamics of excited-state intramolecular proton transfer reactions in piroxicam. Role of triplet states

Science.gov (United States)

Cho, Dae Won; Kim, Yong Hee; Yoon, Minjoong; Jeoung, Sae Chae; Kim, Dongho

1994-08-01

The picosecond time-resolved fluorescence and transient absorption behavior of piroxicam at room temperature are reported. The keto tautomer in the excited singlet state ( 1K*) formed via the fast intramolecular proton transfer (≈ 20 ps) is observed. The short-lived (7.5 ns) triplet state of keto tauomer ( 3K*) is generated from 1K * in toluene whereas it is hardly observed in ethanol. Consequently, rapid reverse proton transfer takes place from 3K * to the enol triplet state ( 3E *.

Time-resolved fluorescence monitoring of cholesterol in peripheral blood mononuclear cells

Science.gov (United States)

Martinakova, Z.; Horilova, J.; Lajdova, I.; Marcek Chorvatova, A.

2014-12-01

Precise evaluation of intracellular cholesterol distribution is crucial for improving diagnostics of diseased states associated with cholesterol alteration. Time-resolved fluorescence techniques are tested for non-invasive investigation of cholesterol in living cells. Fluorescent probe NBD attached to cholesterol was employed to evaluate cholesterol distribution in peripheral blood mononuclear cells (PBMC) isolated from the human blood. Fluorescence Lifetime Imaging Microscopy (FLIM) was successfully applied to simultaneously monitor the spatial distribution and the timeresolved characteristics of the NBD-cholesterol fluorescence in PBMC. Gathered data are the first step in the development of a new perspective non-invasive diagnostic method for evaluation of cholesterol modifications in diseases associated with disorders of lipid metabolism.

On the importance of an accurate representation of the initial state of the system in classical dynamics simulations

Science.gov (United States)

García-Vela, A.

2000-05-01

A definition of a quantum-type phase-space distribution is proposed in order to represent the initial state of the system in a classical dynamics simulation. The central idea is to define an initial quantum phase-space state of the system as the direct product of the coordinate and momentum representations of the quantum initial state. The phase-space distribution is then obtained as the square modulus of this phase-space state. The resulting phase-space distribution closely resembles the quantum nature of the system initial state. The initial conditions are sampled with the distribution, using a grid technique in phase space. With this type of sampling the distribution of initial conditions reproduces more faithfully the shape of the original phase-space distribution. The method is applied to generate initial conditions describing the three-dimensional state of the Ar-HCl cluster prepared by ultraviolet excitation. The photodissociation dynamics is simulated by classical trajectories, and the results are compared with those of a wave packet calculation. The classical and quantum descriptions are found in good agreement for those dynamical events less subject to quantum effects. The classical result fails to reproduce the quantum mechanical one for the more strongly quantum features of the dynamics. The properties and applicability of the phase-space distribution and the sampling technique proposed are discussed.

Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

International Nuclear Information System (INIS)

Ankjaergaard, C.

2010-02-01

Thermoluminescence (TL) and optically stimulated luminescence (OSL) from quartz and feldspar are widely used in accident dosimetry and luminescence dating. In order to improve already existing methods or to develop new methods towards extending the current limits of the technique, it is important to understand the charge movement within these materials. Earlier studies have primarily focussed on examination of the trap behaviour; however, this only tells half of the story as OSL is a combination of charge stimulation and recombination. By using time-resolved OSL (TR-OSL), one can directly examine the recombination route(s), and thus obtain insight into the other half of the process involved in luminescence emission. This thesis studies the TR-OSL and optically stimulated phosphorescence signals from quartz and feldspars spanning several orders of magnitude in time (few ns to the seconds time scale) in order to identify various charge transport mechanisms in the different time regimes. The techniques employed are time-resolved OSL, continuous-wave OSL, TL, optically stimulated exo-electron (OSE) emission and time-resolved OSE. These different techniques are used in combination with variable thermal or optical stimulation energy. The thesis first delves into three main methodological developments, namely (i) research and development of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration for the best separation of quartz OSL from a mixed quarts-feldspar sample. It then proceeds to study the different charge transport mechanisms subsequent to an optical stimulation pulse in quartz and feldspars. The results obtained for quartz conclude that the main lifetime component in quartz represents an excited state lifetime of the recombination centre, and the more slowly decaying components on the millisecond to seconds time scale arise from charge recycling

Understanding optically stimulated charge movement in quartz and feldspar using time-resolved measurements

Energy Technology Data Exchange (ETDEWEB)

Ankjaergaard, C.

2010-02-15

Thermoluminescence (TL) and optically stimulated luminescence (OSL) from quartz and feldspar are widely used in accident dosimetry and luminescence dating. In order to improve already existing methods or to develop new methods towards extending the current limits of the technique, it is important to understand the charge movement within these materials. Earlier studies have primarily focussed on examination of the trap behaviour; however, this only tells half of the story as OSL is a combination of charge stimulation and recombination. By using time-resolved OSL (TR-OSL), one can directly examine the recombination route(s), and thus obtain insight into the other half of the process involved in luminescence emission. This thesis studies the TR-OSL and optically stimulated phosphorescence signals from quartz and feldspars spanning several orders of magnitude in time (few ns to the seconds time scale) in order to identify various charge transport mechanisms in the different time regimes. The techniques employed are time-resolved OSL, continuous-wave OSL, TL, optically stimulated exo-electron (OSE) emission and time-resolved OSE. These different techniques are used in combination with variable thermal or optical stimulation energy. The thesis first delves into three main methodological developments, namely (i) research and development of the equipment for TR-OSL measurements, (ii) finding the best method for multiple-exponential analysis of a TR-OSL curve, and (iii) optimisation of the pulsing configuration for the best separation of quartz OSL from a mixed quarts-feldspar sample. It then proceeds to study the different charge transport mechanisms subsequent to an optical stimulation pulse in quartz and feldspars. The results obtained for quartz conclude that the main lifetime component in quartz represents an excited state lifetime of the recombination centre, and the more slowly decaying components on the millisecond to seconds time scale arise from charge recycling

The electronic structure of clean and adsorbate-covered Bi2Se3: an angle-resolved photoemission study

DEFF Research Database (Denmark)

Bianchi, Marco; Hatch, Richard; Guan, Dandan

2012-01-01

Angle-resolved photoelectron spectroscopy is used for a detailed study of the electronic structure of the topological insulator Bi2Se3. Nominally stoichiometric and calcium-doped samples were investigated. The pristine surface shows the topological surface state in the bulk band gap. As time passes....... For a sufficiently strong band bending, additional states appear at the Fermi level. These are interpreted as quantized conduction band states. For large band bendings, these states are found to undergo a strong Rashba splitting. The formation of quantum well states is also observed for the valence band states......, the Dirac point moves to higher binding energies, indicating an increasingly strong downward bending of the bands near the surface. This time-dependent band bending is related to a contamination of the surface and can be accelerated by intentionally exposing the surface to carbon monoxide and other species...

Time-resolved Femtosecond Photon Echo Probes Bimodal Solvent Dynamics

NARCIS (Netherlands)

Pshenichnikov, M.S; Duppen, K.; Wiersma, D. A.

1995-01-01

We report on time-resolved femtosecond photon echo experiments of a dye molecule in a polar solution. The photon echo is time resolved by mixing the echo with a femtosecond gate pulse in a nonlinear crystal. It is shown that the temporal profile of the photon echo allows separation of the

5 K extended X-ray absorption fine structure and 40 K 10-s resolved extended X-ray absorption fine structure studies of photolyzed carboxymyoglobin

International Nuclear Information System (INIS)

Teng, T.Y.; Huang, H.W.; Olah, G.A.

1987-01-01

A previous extended X-ray absorption fine structure (EXAFS) study of photolyzed carboxymyoglobin (MbCO) has provoked much discussion on the heme structure of the photoproduct (Mb*CO). The EXAFS interpretation that the Fe-Co distance increases by no more than 0.05 A following photodissociation has been regarded as inconsistent with optical, infrared, and magnetic susceptibility studies. The present experiment was performed with well-characterized dry film samples in which MbCO molecules were embedded in a poly(vinyl alcohol) matrix. The sample had a high protein concentration (12 mM) to yield adequate EXAFS signals but was very thin (40 μm) so that complete photolysis could be easily achieved by a single flash from a xenon lamp. Although the electronic state of Mb*CO resembles that of deoxymyoglobin (deoxy-Mb), direct comparison of EXAFS spectra indicates that structurally Mb*CO is much closer to MbCO than to deoxy-Mb. Our EXAFS analysis shows that photolysis of MbCO at 5 K leads to a stable intermediate state in which CO has moved away from iron by a distance of 0.27-0.45 A, but the 5-coordinate heme structure is strained in a form similar to that of MbCO; the resolution of the CO position depends on the structure parameters of MbCO which we use as a reference for the analysis of Mb*CO. At 40 K, from 1 to 10 s after photolysis, 42% of the photoproduct has relaxed to the ground state, and the EXAFS spectrum of the remaining photoproduct is indistinguishable from that of the 5 K photoproduct

Highly time-resolved imaging of combustion and pyrolysis product concentrations in solid fuel combustion: NO formation in a burning cigarette.

Science.gov (United States)

Zimmermann, Ralf; Hertz-Schünemann, Romy; Ehlert, Sven; Liu, Chuan; McAdam, Kevin; Baker, Richard; Streibel, Thorsten

2015-02-03

The highly dynamic, heterogeneous combustion process within a burning cigarette was investigated by a miniaturized extractive sampling probe (microprobe) coupled to photoionization mass spectrometry using soft laser single photon ionization (SPI) for online real-time detection of molecular ions of combustion and pyrolysis products. Research cigarettes smoked by a smoking machine are used as a reproducible model system for solid-state biomass combustion, which up to now is not addressable by current combustion-diagnostic tools. By combining repetitively recorded online measurement sequences from different sampling locations in an imaging approach, highly time- and space-resolved quantitative distribution maps of, e.g., nitrogen monoxide, benzene, and oxygen concentrations were obtained at a near microscopic level. The obtained quantitative distribution maps represent a time-resolved, movie-like imaging of the respective compound's formation and destruction zones in the various combustion and pyrolysis regions of a cigarette during puffing. Furthermore, spatially resolved kinetic data were ascertainable. The here demonstrated methodology can also be applied to various heterogenic combustion/pyrolysis or reaction model systems, such as fossil- or biomass-fuel pellet combustion or to a positional resolved analysis of heterogenic catalytic reactions.

The Resolved Stellar Populations Early Release Science Program

Science.gov (United States)

Gilbert, Karoline; Weisz, Daniel; Resolved Stellar Populations ERS Program Team

2018-06-01

The Resolved Stellar Populations Early Release Science Program (PI D. Weisz) will observe Local Group targets covering a range of stellar density and star formation histories, including a globular cluster, and ultra-faint dwarf galaxy, and a star-forming dwarf galaxy. Using observations of these diverse targets we will explore a broad science program: we will measure star formation histories, the sub-solar stellar initial mass function, and proper motions, perform studies of evolved stars, and map extinction in the target fields. Our observations will be of high archival value for other science such as calibrating stellar evolution models, studying variable stars, and searching for metal-poor stars. We will determine optimal observational setups and develop data reduction techniques that will be common to JWST studies of resolved stellar populations. We will also design, test, and release point spread function (PSF) fitting software specific to NIRCam and NIRISS, required for the crowded stellar regime. Prior to the Cycle 2 Call for Proposals, we will release PSF fitting software, matched HST and JWST catalogs, and clear documentation and step-by-step tutorials (such as Jupyter notebooks) for reducing crowded stellar field data and producing resolved stellar photometry catalogs, as well as for specific resolved stellar photometry science applications.

Solar-pumped gas laser development

Science.gov (United States)

Wilson, J. W.

1981-01-01

The direct conversion of solar radiation into an inverted population for extraction in an optical cavity holds promise as a relatively simple system design. Broad-band photoabsorption in the visible or near-UV range is required to excite large volumes of gas and to ensure good solar absorption efficiency. The state excited must be a metastable state which is not quenched by the parent gas. The emission bandwidth must be less than approximately 10 A. The system should show chemical reversibility and an insensitivity to increasing temperature. Other properties such as good quantum efficiency and kinetic efficiency are also implied. A search of electronic-vibrational transitions in diatomic molecules satisfying these conditions is now in progress. A photodissociation-pumped atomic iodine laser is now being tested under solar pumping conditions. Photodissociation studies for thallium spin-flip metastable formation will begin in the near future.

CMOS Time-Resolved, Contact, and Multispectral Fluorescence Imaging for DNA Molecular Diagnostics

Directory of Open Access Journals (Sweden)

Nan Guo

2014-10-01

Full Text Available Instrumental limitations such as bulkiness and high cost prevent the fluorescence technique from becoming ubiquitous for point-of-care deoxyribonucleic acid (DNA detection and other in-field molecular diagnostics applications. The complimentary metal-oxide-semiconductor (CMOS technology, as benefited from process scaling, provides several advanced capabilities such as high integration density, high-resolution signal processing, and low power consumption, enabling sensitive, integrated, and low-cost fluorescence analytical platforms. In this paper, CMOS time-resolved, contact, and multispectral imaging are reviewed. Recently reported CMOS fluorescence analysis microsystem prototypes are surveyed to highlight the present state of the art.

Analysis of time- and space-resolved Na-, Ne-, and F-like emission from a laser-produced bromine plasma

International Nuclear Information System (INIS)

Goldstein, W.H.; Young, B.K.F.; Osterheld, A.L.; Stewart, R.E.; Walling, R.S.; Bar-Shalom, A.

1991-01-01

Advances in the efficiency and accuracy of computational atomic physics and collisional radiative modeling promise to place the analysis and diagnostic application of L-shell emission on a par with the simpler K-shell regime. Coincident improvements in spectroscopic plasma measurements yield optically thin emission spectra from small, homogeneous regions of plasma, localized both in space and time. Together, these developments can severely test models for high-density, high-temperature plasma formation and evolution, and non-LTE atomic kinetics. In this paper we present highly resolved measurements of n=3 to n=2 X-ray line emission from a laser-produced bromine micro plasma. The emission is both space- and time-resolved, allowing us to apply simple, steady-state, 0-dimensional spectroscopic models to the analysis. These relativistic, multi-configurational, distorted wave collisional-radiative models were created using the HULLAC atomic physics package. Using these models, we have analyzed the F-like, Ne-like and Na-like (satellite) spectra with respect to temperature, density and charge-state distribution. This procedure leads to a full characterization of the plasma conditions. 9 refs., 3 figs

Time-resolved brightness measurements by streaking

Science.gov (United States)

Torrance, Joshua S.; Speirs, Rory W.; McCulloch, Andrew J.; Scholten, Robert E.

2018-03-01

Brightness is a key figure of merit for charged particle beams, and time-resolved brightness measurements can elucidate the processes involved in beam creation and manipulation. Here we report on a simple, robust, and widely applicable method for the measurement of beam brightness with temporal resolution by streaking one-dimensional pepperpots, and demonstrate the technique to characterize electron bunches produced from a cold-atom electron source. We demonstrate brightness measurements with 145 ps temporal resolution and a minimum resolvable emittance of 40 nm rad. This technique provides an efficient method of exploring source parameters and will prove useful for examining the efficacy of techniques to counter space-charge expansion, a critical hurdle to achieving single-shot imaging of atomic scale targets.

Deflection evaluation using time-resolved radiography

International Nuclear Information System (INIS)

Fry, D.A.; Lucero, J.P.

1990-01-01

Time-resolved radiography is the creation of an x-ray image for which both the start-exposure and stop-exposure times are known with respect to the event under study. The combination of image and timing are used to derive information about the event. The authors have applied time-resolved radiography to evaluate motions of explosive-driven events. In the particular application discussed in this paper, the author's intent is to measure maximum deflections of the components involved. Exposures are made during the time just before to just after the event of interest occurs. A smear or blur of motion out to its furthest extent is recorded on the image. Comparison of the dynamic images with static images allows deflection measurements to be made

Strongly nonexponential time-resolved fluorescence of quantum-dot ensembles in three-dimensional photonic crystals

DEFF Research Database (Denmark)

Nikolaev, Ivan S.; Lodahl, Peter; van Driel, A. Floris

2007-01-01

We observe experimentally that ensembles of quantum dots in three-dimensional 3D photonic crystals reveal strongly nonexponential time-resolved emission. These complex emission decay curves are analyzed with a continuous distribution of decay rates. The log-normal distribution describes the decays...... parameter. This interpretation qualitatively agrees with the calculations of the 3D projected local density of states. We therefore conclude that fluorescence decay of ensembles of quantum dots is highly nonexponential to an extent that is controlled by photonic crystals....

Depth-resolved incoherent and coherent wide-field high-content imaging (Conference Presentation)

Science.gov (United States)

So, Peter T.

2016-03-01

Recent advances in depth-resolved wide-field imaging technique has enabled many high throughput applications in biology and medicine. Depth resolved imaging of incoherent signals can be readily accomplished with structured light illumination or nonlinear temporal focusing. The integration of these high throughput systems with novel spectroscopic resolving elements further enable high-content information extraction. We will introduce a novel near common-path interferometer and demonstrate its uses in toxicology and cancer biology applications. The extension of incoherent depth-resolved wide-field imaging to coherent modality is non-trivial. Here, we will cover recent advances in wide-field 3D resolved mapping of refractive index, absorbance, and vibronic components in biological specimens.

Time-resolved emission from laser-ablated uranium

International Nuclear Information System (INIS)

Stoffels, E.; Mullen, J. van der; Weijer, P. van de

1991-01-01

Time-resolved emission spectra from the plasma, induced by laser ablation of uranium samples have been studied. The dependence of the emission intensity on time is strongly affected by the nature and pressure of the buffer gas. Air and argon have been used in the pressure range 0.002 to 5 mbar. The emission intensity as a function of time displays three maxima, indicating that three different processes within the expanding plasma plume are involved. On basis of the time-resolved spectra we propose a model that explains qualitatively the phenomena that are responsible for this time behaviour. (author)

Spatially Resolved Isotopic Source Signatures of Wetland Methane Emissions

Science.gov (United States)

Ganesan, A. L.; Stell, A. C.; Gedney, N.; Comyn-Platt, E.; Hayman, G.; Rigby, M.; Poulter, B.; Hornibrook, E. R. C.

2018-04-01

We present the first spatially resolved wetland δ13C(CH4) source signature map based on data characterizing wetland ecosystems and demonstrate good agreement with wetland signatures derived from atmospheric observations. The source signature map resolves a latitudinal difference of 10‰ between northern high-latitude (mean -67.8‰) and tropical (mean -56.7‰) wetlands and shows significant regional variations on top of the latitudinal gradient. We assess the errors in inverse modeling studies aiming to separate CH4 sources and sinks by comparing atmospheric δ13C(CH4) derived using our spatially resolved map against the common assumption of globally uniform wetland δ13C(CH4) signature. We find a larger interhemispheric gradient, a larger high-latitude seasonal cycle, and smaller trend over the period 2000-2012. The implication is that erroneous CH4 fluxes would be derived to compensate for the biases imposed by not utilizing spatially resolved signatures for the largest source of CH4 emissions. These biases are significant when compared to the size of observed signals.

Ultrafast time-resolved spectroscopy of xanthophylls at low temperature.

Science.gov (United States)

Cong, Hong; Niedzwiedzki, Dariusz M; Gibson, George N; Frank, Harry A

2008-03-20

Many of the spectroscopic features and photophysical properties of xanthophylls and their role in energy transfer to chlorophyll can be accounted for on the basis of a three-state model. The characteristically strong visible absorption of xanthophylls is associated with a transition from the ground state S0 (1(1)Ag-) to the S2 (1(1)Bu+) excited state. The lowest lying singlet state denoted S1 (2(1)Ag-), is a state into which absorption from the ground state is symmetry forbidden. Ultrafast optical spectroscopic studies and quantum computations have suggested the presence of additional excited singlet states in the vicinity of S1 (2(1)Ag-) and S2 (1(1)Bu+). One of these is denoted S* and has been suggested in previous work to be associated with a twisted molecular conformation of the molecule in the S1 (2(1)Ag-) state. In this work, we present the results of a spectroscopic investigation of three major xanthophylls from higher plants: violaxanthin, lutein, and zeaxanthin. These molecules have systematically increasing extents of pi-electron conjugation from nine to eleven conjugated carbon-carbon double bonds. All-trans isomers of the molecules were purified by high-performance liquid chromatography (HPLC) and studied by steady-state and ultrafast time-resolved optical spectroscopy at 77 K. Analysis of the data using global fitting techniques has revealed the inherent spectral properties and ultrafast dynamics of the excited singlet states of each of the molecules. Five different global fitting models were tested, and it was found that the data are best explained using a kinetic model whereby photoexcitation results in the promotion of the molecule into the S2 (1(1)Bu+) state that subsequently undergoes decay to a vibrationally hot S1 (1(1)Ag-) state and with the exception of violaxanthin also to the S* state. The vibrationally hot S1 (1(1)Ag-) state then cools to a vibrationally relaxed S1 (2(1)Ag-) state in less than a picosecond. It was also found that a portion

A Theoretical Study of the Photodissociation Mechanism of Cyanoacetylene in Its Lowest Singlet and Triplet Excited States

Science.gov (United States)

Luo, Cheng; Du, Wei-Na; Duan, Xue-Mei; Li, Ze-Sheng

2008-11-01

Cyanoacetylene (H5-C4 ≡ C3-C2 ≡ N1) is a minor constituent of the atmosphere of Titan, and its photochemistry plays an important role in the formation of the haze surrounding the satellite. In this paper, the complete active space self-consistent field (CASSCF) and multiconfigurational second-order perturbation (CASPT2) approaches are employed to investigate the photochemical processes for cyanoacetylene in its first singlet and triplet excited states with the cc-pVTZ basis set. Fissions of the C4-H5 and C2-C3 bonds in S1 yield H(2S) + CCCN(A2Π) and HCC(A2Π) + CN(X2Σ+), respectively. In T1, the corresponding dissociation products are H(2S) + CCCN(X2Σ+) and HCC(X2Σ) + CN(X2Σ+). At the CASPT2(14,13)//CASSCF(14,13) + ZPE level, the barriers for the adiabatic dissociation of the C4-H5 and C2-C3 bonds are 6.11 and 6.94 eV in S1 and 5.71 and 6.39 eV in T1, respectively, taking the energy of S0 minimum as reference. Based on the calculated potential energy surfaces, the existence of a metastable excited molecule is anticipated upon 260-230 nm photoexcitation, which provides a probable approach for cyanoacetylene to polymerize. The internal conversion (IC) process through vibronic interaction followed by C4-H5 fission in the ground state is found to account for the observed diffuse character in the UV absorption spectrum below 240 nm.

Analysis of a photon number resolving detector based on fluorescence readout of an ion Coulomb crystal quantum memory inside an optical cavity

DEFF Research Database (Denmark)

Clausen, Christoph; Sangouard, N.; Drewsen, M.

2013-01-01

The ability to detect single photons with a high efficiency is a crucial requirement for various quantum information applications. By combining the storage process of a quantum memory for photons with fluorescence-based quantum state measurement, it is, in principle, possible to achieve high......-efficiency photon counting in large ensembles of atoms. The large number of atoms can, however, pose significant problems in terms of noise stemming from imperfect initial state preparation and off-resonant fluorescence. We identify and analyse a concrete implementation of a photon number resolving detector based...... larger than 93%. Moderate experimental parameters allow for repetition rates of about 3 kHz, limited by the time needed for fluorescence collection and re-cooling of the ions between trials. Our analysis may lead to the first implementation of a photon number resolving detector in atomic ensembles....

An ultrafast angle-resolved photoemission apparatus for measuring complex materials

Science.gov (United States)

Smallwood, Christopher L.; Jozwiak, Christopher; Zhang, Wentao; Lanzara, Alessandra

2012-12-01

We present technical specifications for a high resolution time- and angle-resolved photoemission spectroscopy setup based on a hemispherical electron analyzer and cavity-dumped solid state Ti:sapphire laser used to generate pump and probe beams, respectively, at 1.48 and 5.93 eV. The pulse repetition rate can be tuned from 209 Hz to 54.3 MHz. Under typical operating settings the system has an overall energy resolution of 23 meV, an overall momentum resolution of 0.003 Å-1, and an overall time resolution of 310 fs. We illustrate the system capabilities with representative data on the cuprate superconductor Bi2Sr2CaCu2O8+δ. The descriptions and analyses presented here will inform new developments in ultrafast electron spectroscopy.

Indoor Measurement of Angle Resolved Light Absorption by Black Silicon

DEFF Research Database (Denmark)

Amdemeskel, Mekbib Wubishet; Iandolo, Beniamino; Davidsen, Rasmus Schmidt

2017-01-01

Angle resolved optical spectroscopy of photovoltaic (PV) samples gives crucial information on PV panels under realistic working conditions. Here, we introduce measurements of angle resolved light absorption by PV cells, performed indoors using a collimated high radiance broadband light source. Our...... indoor method offers a significant simplification as compared to measurements by solar trackers. As a proof-of-concept demonstration, we show characterization of black silicon solar cells. The experimental results showed stable and reliable optical responses that makes our setup suitable for indoor......, angle resolved characterization of solar cells....

Time-resolved studies. Ch. 9

International Nuclear Information System (INIS)

Mills, Dennis M.; Argonne National Lab., IL

1991-01-01

Synchrotron radiation, with its unique properties, offers a tool to extend X-ray measurements from the static to the time-resolved regime. The most straight-forward application of synchrotron radiation to the study of transient phenomena is directly through the possibility of decreased data-collection times via the enormous increase in flux over that of a laboratory X-ray system. Even further increases in intensity can be obtained through the use of novel X-ray optical devices. Wide-bandpass monochromators, e.g., that utilize the continuous spectral distribution of synchrotron radiation, can increase flux on the sample several orders of magnitude over conventional X-ray optical systems thereby allowing a further shortening of the data-collection time. Another approach that uses the continuous spectral nature of synchrotron radiation to decrease data-collection times is the 'parallel data collection' method. Using this technique, intensities as a function of X-ray energy are recorded simultaneously for all energies rather than sequentially recording data at each energy, allowing for a dramatic decrease in data-collection time. Perhaps the most exciting advances in time-resolved X-ray studies will be made by those methods that exploit the pulsed nature of the radiation emitted from storage rings. Pulsed techniques have had an enormous impact in the study of the temporal evolution of transient phenomena. The extension from continuous to modulated sources for use in time-resolved work has been carried over in a host of fields that use both pulsed particle and pulsed electro-magnetic beams. In this chapter the new experimental techniques are reviewed and illustrated with some experiments. (author). 98 refs.; 20 figs.; 5 tabs

Time-resolved tunable diode laser absorption spectroscopy of excited argon and ground-state titanium atoms in pulsed magnetron discharges

Czech Academy of Sciences Publication Activity Database

Sushkov, V.; Do, H.T.; Čada, Martin; Hubička, Zdeněk; Hippler, R.

2013-01-01

Roč. 22, č. 1 (2013), 1-10 ISSN 0963-0252 R&D Projects: GA ČR(CZ) GAP205/11/0386; GA ČR GAP108/12/2104 Institutional research plan: CEZ:AV0Z10100522 Keywords : absorption spectroscopy * diode laser * magnetron * argon metastable * HiPIMS * titanium * time-resolved Subject RIV: BH - Optics, Masers, Lasers Impact factor: 3.056, year: 2013 http://iopscience.iop.org/0963-0252/22/1/015002/

Dynamics of Spontaneous Emission Controlled by Local Density of States in Photonic Crystals

DEFF Research Database (Denmark)

Lodahl, Peter; Nikolaev, Ivan S.; van Driel, A. Floris

2006-01-01

We have measured time-resolved spontaneous emission from quantum dots in 3D photonic crystals. Due to the spatially dependent local density of states, the distribution of decay rates varies strongly with the photonic crystal lattice parameter.......We have measured time-resolved spontaneous emission from quantum dots in 3D photonic crystals. Due to the spatially dependent local density of states, the distribution of decay rates varies strongly with the photonic crystal lattice parameter....

Magneto-electronic properties and spin-resolved I-V curves of a Co/GeSe heterojunction diode: an ab initio study

Science.gov (United States)

Makinistian, Leonardo; Albanesi, Eduardo A.

2013-06-01

We present ab initio calculations of magnetoelectronic and transport properties of the interface of hcp Cobalt (001) and the intrinsic narrow-gap semiconductor germanium selenide (GeSe). Using a norm-conserving pseudopotentials scheme within DFT, we first model the interface with a supercell approach and focus on the spin-resolved densities of states and the magnetic moment (spin and orbital components) at the different atomic layers that form the device. We also report a series of cuts (perpendicular to the plane of the heterojunction) of the electronic and spin densities showing a slight magnetization of the first layers of the semiconductor. Finally, we model the device with a different scheme: using semiinfinite electrodes connected to the heterojunction. These latter calculations are based upon a nonequilibrium Green's function approach that allows us to explore the spin-resolved electronic transport under a bias voltage (spin-resolved I-V curves), revealing features of potential applicability in spintronics.

Coherent Control of Photofragment Distributions Using Laser Phase Modulation in the Weak-Field Limit

DEFF Research Database (Denmark)

Garcia-Vela, Alberto; Henriksen, Niels Engholm

2015-01-01

The possibility of quantum interference control of the final state distributions of photodissociation fragments by means of pure phase modulation of the pump laser pulse in the weak-field regime is demonstrated theoretically for the first time. The specific application involves realistic wave pac...

Ultrafast time-resolved carotenoid to-bacteriochlorophyll energy transfer in LH2 complexes from photosynthetic bacteria.

Science.gov (United States)

Cong, Hong; Niedzwiedzki, Dariusz M; Gibson, George N; LaFountain, Amy M; Kelsh, Rhiannon M; Gardiner, Alastair T; Cogdell, Richard J; Frank, Harry A

2008-08-28

Steady-state and ultrafast time-resolved optical spectroscopic investigations have been carried out at 293 and 10 K on LH2 pigment-protein complexes isolated from three different strains of photosynthetic bacteria: Rhodobacter (Rb.) sphaeroides G1C, Rb. sphaeroides 2.4.1 (anaerobically and aerobically grown), and Rps. acidophila 10050. The LH2 complexes obtained from these strains contain the carotenoids, neurosporene, spheroidene, spheroidenone, and rhodopin glucoside, respectively. These molecules have a systematically increasing number of pi-electron conjugated carbon-carbon double bonds. Steady-state absorption and fluorescence excitation experiments have revealed that the total efficiency of energy transfer from the carotenoids to bacteriochlorophyll is independent of temperature and nearly constant at approximately 90% for the LH2 complexes containing neurosporene, spheroidene, spheroidenone, but drops to approximately 53% for the complex containing rhodopin glucoside. Ultrafast transient absorption spectra in the near-infrared (NIR) region of the purified carotenoids in solution have revealed the energies of the S1 (2(1)Ag-)-->S2 (1(1)Bu+) excited-state transitions which, when subtracted from the energies of the S0 (1(1)Ag-)-->S2 (1(1)Bu+) transitions determined by steady-state absorption measurements, give precise values for the positions of the S1 (2(1)Ag-) states of the carotenoids. Global fitting of the ultrafast spectral and temporal data sets have revealed the dynamics of the pathways of de-excitation of the carotenoid excited states. The pathways include energy transfer to bacteriochlorophyll, population of the so-called S* state of the carotenoids, and formation of carotenoid radical cations (Car*+). The investigation has found that excitation energy transfer to bacteriochlorophyll is partitioned through the S1 (1(1)Ag-), S2 (1(1)Bu+), and S* states of the different carotenoids to varying degrees. This is understood through a consideration of the

Kinematic equations for resolved-rate control of an industrial robot arm

Science.gov (United States)

Barker, L. K.

1983-01-01

An operator can use kinematic, resolved-rate equations to dynamically control a robot arm by watching its response to commanded inputs. Known resolved-rate equations for the control of a particular six-degree-of-freedom industrial robot arm and proceeds to simplify the equations for faster computations are derived. Methods for controlling the robot arm in regions which normally cause mathematical singularities in the resolved-rate equations are discussed.

Case-resolving capacity of dental care of the Unified Health System: the perception of users in a city in the state of São Paulo, Brazil

Directory of Open Access Journals (Sweden)

Arinilson Moreira Chaves Lima

Full Text Available Abstract The aim of this study was to learn about the users' perceptions concerning the case-resolving capacity of dental care in the Unified Health System and to analyze the associations between solving capacity and both sociodemographic characteristics and access to the service. This was a cross-sectional study with a quantitative approach, in which 461 users responded to individual interviews. The outcome variable was the case-resolving capacity of dental care, obtained through the question: “In your opinion, is the dentist of this health center managing to solve all your oral health problems (Yes/No”. Independent variables were grouped into the following: sociodemographic and related to the access to the service. Most participants reported that their oral health problems were being solved. By using the Poisson regression, the lack of case-resolving capacity was found to be associated to the patients' not considering the dental surgeon's working hours convenient; to the long time they had to wait to get an appointment in the health center; and to the long time they had to wait in the waiting room. The results showed the positive view that users have about the case-resolving capacity of public dental care, and the relationship between access to the service and the said solving capacity.

Photodissociation and stability of carbon clusters; Photodissociation et stabilite d`agregats de carbone

Energy Technology Data Exchange (ETDEWEB)

Bouyer, R.

1995-04-01

This work is devoted to the study of the dissociation of ionised carbon clusters (containing 16 to 36 atoms) after photoexcitation by a UV-visible laser pulse. It contributes to experimental studies on formation mechanisms of carbon clusters, and particularly fullerenes. Its first aim is the knowledge of the internal energy of the clusters before dissociation. In the first part, a general overview summarizes the theoretical and experimental studies devoted to energetics (structure, stability, dissociation) of carbon clusters containing less than 60 atoms. In the second part, two techniques for producing mass-selected carbon clusters are described. The particular characteristics for such a production in a direct vaporization source are compared to those in a collisional-cooled source. The question of stability of intermediate-size clusters is asked. We study the photoabsorption spectroscopy of carbon clusters in the third part. A model for sequential absorption of several photons is developed, and used to analyze cluster dissociation versus the photoexcitation laser fluence. The absolute photoabsorption cross sections, and the number of absorbed photons are deduced. For some cluster sizes, laser wavelength scanning leads to evidence for existence of several clusters structures (or so-called isomers). The last part deals with photo dissociation mechanisms. Dissociation is found to occur after single-photon absorption, or after vibrational heating of the clusters. In that latter case, a statistical model including restricted intramolecular vibrational energy redistribution is used to calculate dissociation energies from measured fragmentation times of well-defined internal energy states. These energies, which are characteristic of cyclic structures, are then used to a better understanding of carbon cluster formation in a direct vaporization source. (Author). 76 refs., 63 figs., 23 tabs.

A new approach to molecular dynamics with non-adiabatic and spin-orbit effects with applications to QM/MM simulations of thiophene and selenophene

Czech Academy of Sciences Publication Activity Database

Pederzoli, Marek; Pittner, Jiří

2017-01-01

Roč. 146, č. 11 (2017), č. článku 114101. ISSN 0021-9606 R&D Projects: GA ČR(CZ) GAP208/12/0559 Institutional support: RVO:61388955 Keywords : configuration-interaction method * potential-energy surfaces * excited-state dynamics * photodissociation dynamics * electronic states * quantum dynamics Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 2.965, year: 2016

Time-resolved blood flow measurement in the in vivo mouse model by optical frequency domain imaging

Science.gov (United States)

Walther, Julia; Mueller, Gregor; Meissner, Sven; Cimalla, Peter; Homann, Hanno; Morawietz, Henning; Koch, Edmund

2009-07-01

In this study, we demonstrate that phase-resolved Doppler optical frequency domain imaging (OFDI) is very suitable to quantify the pulsatile blood flow within a vasodynamic measurement in the in vivo mouse model. For this, an OFDI-system with a read-out rate of 20 kHz and a center wavelength of 1320 nm has been used to image the time-resolved murine blood flow in 300 μμm vessels. Because OFDI is less sensitive to fringe washout due to axial sample motion, it is applied to analyze the blood flow velocities and the vascular dynamics in six-week-old C57BL/6 mice compared to one of the LDLR knockout strain kept under sedentary conditions or with access to voluntary wheel running. We have shown that the systolic as well as the diastolic phase of the pulsatile arterial blood flow can be well identified at each vasodynamic state. Furthermore, the changes of the flow velocities after vasoconstriction and -dilation were presented and interpreted in the entire physiological context. With this, the combined measurement of time-resolved blood flow and vessel diameter provides the basis to analyze the vascular function and its influence on the blood flow of small arteries of different mouse strains in response to different life styles.

Photoemission electronic states of epitaxially grown magnetite films

International Nuclear Information System (INIS)

Zalecki, R.; Kolodziejczyk, A.; Korecki, J.; Spiridis, N.; Zajac, M.; Kozlowski, A.; Kakol, Z.; Antolak, D.

2007-01-01

The valence band photoemission spectra of epitaxially grown 300 A single crystalline magnetite films were measured by the angle-resolved ultraviolet photoemission spectroscopy (ARUPS) at 300 K. The samples were grown either on MgO(0 0 1) (B termination) or on (0 0 1) Fe (iron-rich A termination), thus intentionally presenting different surface stoichiometry, i.e. also different surface electronic states. Four main features of the electron photoemission at about -1.0, -3.0, -5.5 and -10.0 eV below a chemical potential show systematic differences for two terminations; this difference depends on the electron outgoing angle. Our studies confirm sensitivity of angle resolved PES technique on subtleties of surface states

Electronic structure, Dirac points and Fermi arc surface states in three-dimensional Dirac semimetal Na3Bi from angle-resolved photoemission spectroscopy

International Nuclear Information System (INIS)

Liang Aiji; Chen Chaoyu; Wang Zhijun; Shi Youguo; Feng Ya; Yi Hemian; Xie Zhuojin; He Shaolong; He Junfeng; Peng Yingying; Liu Yan; Liu Defa; Hu Cheng; Zhao Lin; Liu Guodong; Dong Xiaoli; Zhang Jun; Nakatake, M; Iwasawa, H; Shimada, K

2016-01-01

The three-dimensional (3D) Dirac semimetals have linearly dispersive 3D Dirac nodes where the conduction band and valence band are connected. They have isolated 3D Dirac nodes in the whole Brillouin zone and can be viewed as a 3D counterpart of graphene. Recent theoretical calculations and experimental results indicate that the 3D Dirac semimetal state can be realized in a simple stoichiometric compound A 3 Bi ( A = Na, K, Rb). Here we report comprehensive high-resolution angle-resolved photoemission (ARPES) measurements on the two cleaved surfaces, (001) and (100), of Na 3 Bi. On the (001) surface, by comparison with theoretical calculations, we provide a proper assignment of the observed bands, and in particular, pinpoint the band that is responsible for the formation of the three-dimensional Dirac cones. We observe clear evidence of 3D Dirac cones in the three-dimensional momentum space by directly measuring on the k x – k y plane and by varying the photon energy to get access to different out-of-plane k z s. In addition, we reveal new features around the Brillouin zone corners that may be related with surface reconstruction. On the (100) surface, our ARPES measurements over a large momentum space raise an issue on the selection of the basic Brillouin zone in the (100) plane. We directly observe two isolated 3D Dirac nodes on the (100) surface. We observe the signature of the Fermi-arc surface states connecting the two 3D Dirac nodes that extend to a binding energy of ∼150 meV before merging into the bulk band. Our observations constitute strong evidence on the existence of the Dirac semimetal state in Na 3 Bi that are consistent with previous theoretical and experimental work. In addition, our results provide new information to clarify on the nature of the band that forms the 3D Dirac cones, on the possible formation of surface reconstruction of the (001) surface, and on the issue of basic Brillouin zone selection for the (100) surface. (rapid communication)

Time resolved measurements of cathode fall in high frequency fluorescent lamps

International Nuclear Information System (INIS)

Hadrath, S; Garner, R C; Lieder, G H; Ehlbeck, J

2007-01-01

Measurements are presented of the time resolved cathode and anode falls of high frequency fluorescent lamps for a range of discharge currents typically encountered in dimming mode. Measurements were performed with the movable anode technique. Supporting spectroscopic emission measurements were made of key transitions (argon 420.1 nm and mercury 435.8 nm), whose onset coincide with cathode fall equalling the value associated with the energy, relative to the ground state, of the upper level of the respective transition. The measurements are in general agreement with the well-known understanding of dimmed lamp operation: peak cathode fall decreases with increasing lamp current and with increasing auxiliary coil heating. However, the time dependence of the measurements offers additional insight

Highly-resolving Rutherford-scattering spectroscopy with heavy ions

International Nuclear Information System (INIS)

Klein, C.

2003-10-01

in the present thesis for the first time the Browne-Buechner spectrometer for the highly resolving ion-beam analysis in the ion beam center Rossendorf is completely presented. A main topic of this theis lied in the apparative construction and the taking-into-operation of the spectrometer and the scattering chamber including the facilities for the sample treatment and characterization. In the framework of this thesis for the chosen measurement arrangement the experimental conditions were elaborated, which allow the routine-like application of the spectrometer for analyses of thin-film systems. for C and Li ions as incident particles especially the straggling was more precisely determined in a large range of materials. By means of the spectrometer also the interaction of the ion with the solid respectively single atoms on its surface could be studied. For the first time the mean charge-state after the single collision on a gold atom was determined for differently heavy ions in a wide energy range

Spin-resolved photoelectron spectroscopy using femtosecond extreme ultraviolet light pulses from high-order harmonic generation

Energy Technology Data Exchange (ETDEWEB)

Plötzing, M.; Adam, R., E-mail: r.adam@fz-juelich.de; Weier, C.; Plucinski, L.; Schneider, C. M. [Forschungszentrum Jülich GmbH, Peter Grünberg Institut (PGI-6), 52425 Jülich (Germany); Eich, S.; Emmerich, S.; Rollinger, M.; Aeschlimann, M. [University of Kaiserslautern and Research Center OPTIMAS, 67663 Kaiserslautern (Germany); Mathias, S. [Georg-August-Universität Göttingen, I. Physikalisches Institut, 37077 Göttingen (Germany)

2016-04-15

The fundamental mechanism responsible for optically induced magnetization dynamics in ferromagnetic thin films has been under intense debate since almost two decades. Currently, numerous competing theoretical models are in strong need for a decisive experimental confirmation such as monitoring the triggered changes in the spin-dependent band structure on ultrashort time scales. Our approach explores the possibility of observing femtosecond band structure dynamics by giving access to extended parts of the Brillouin zone in a simultaneously time-, energy- and spin-resolved photoemission experiment. For this purpose, our setup uses a state-of-the-art, highly efficient spin detector and ultrashort, extreme ultraviolet light pulses created by laser-based high-order harmonic generation. In this paper, we present the setup and first spin-resolved spectra obtained with our experiment within an acquisition time short enough to allow pump-probe studies. Further, we characterize the influence of the excitation with femtosecond extreme ultraviolet pulses by comparing the results with data acquired using a continuous wave light source with similar photon energy. In addition, changes in the spectra induced by vacuum space-charge effects due to both the extreme ultraviolet probe- and near-infrared pump-pulses are studied by analyzing the resulting spectral distortions. The combination of energy resolution and electron count rate achieved in our setup confirms its suitability for spin-resolved studies of the band structure on ultrashort time scales.

Resolving Ethical Issues at School

Science.gov (United States)

Benninga, Jacques S.

2013-01-01

Although ethical dilemmas are a constant in teachers' lives, the profession has offered little in the way of training to help teachers address such issues. This paper presents a framework, based on developmental theory, for resolving professional ethical dilemmas. The Four-Component Model of Moral Maturity, when used in conjunction with a…

Resolved resonance parameters for 236Np

International Nuclear Information System (INIS)

Morogovskij, G.B.; Bakhanovich, L.A.

2002-01-01

Multilevel Breit-Wigner parameters were obtained for fission cross-section representation in the 0.01-33 eV energy region from evaluation of a 236 Np experimental fission cross-section in the resolved resonance region. (author)

Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

KAUST Repository

Snellenburg, Joris J.; Laptenok, Sergey P.; DeSa, Richard J.; Naumov, Pance; Solntsev, Kyril M.

2016-01-01

The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.

Excited-State Dynamics of Oxyluciferin in Firefly Luciferase

KAUST Repository

Snellenburg, Joris J.

2016-11-23

The color variations of light emitted by some natural and mutant luciferases are normally attributed to collective factors referred to as microenvironment effects; however, the exact nature of these interactions between the emitting molecule (oxyluciferin) and the active site remains elusive. Although model studies of noncomplexed oxyluciferin and its variants have greatly advanced the understanding of its photochemistry, extrapolation of the conclusions to the real system requires assumptions about the polarity and proticity of the active site. To decipher the intricate excited-state dynamics, global and target analysis is performed here for the first time on the steady-state and time-resolved spectra of firefly oxyluciferin complexed with luciferase from the Japanese firefly (Luciola cruciata). The experimental steady-state and time resolved luminescence spectra of the oxyluciferin/luciferase complex in solution are compared with the broadband time-resolved firefly bioluminescence recorded in vivo. The results demonstrate that de-excitation of the luminophore results in a complex cascade of photoinduced proton transfer processes and can be interpreted by the pH dependence of the emitted light. It is confirmed that proton transfer is the central event in the spectrochemistry of this system for which any assignment of the pH dependent emission to a single chemical species would be an oversimplification.

Selective control of photodissociation in deutereted water molecule HOD

International Nuclear Information System (INIS)

Adhikari, S.; Deshpande, Sarin; Sarma, Manabendra; Kurkal, Vandana; Mishra, M.K.

2006-01-01

Bond dissociation in the deutereted water molecule HOD has been investigated to explore the possibility of selective control of dissociation of O-H and O-D bonds using simple field profiles and initial states that do not require high overtone excitations. Preliminary results indicate that considerable selectivity in dissociation of O-H and O-D bonds can be achieved using fundamental and first overtone excitations only and use of field optimized initial state (FOIST) based scheme with appropriate choice of field parameters and initial states may enhance both selectivity and yield

Band structure and Fermi surface of UPd2Al3 studied by angle-resolved photoemission spectroscopy

International Nuclear Information System (INIS)

Fujimori, Shin-ichi; Saitoh, Yuji; Okane, Tetsuo; Yamagami, Hiroshi; Fujimori, Atsushi; Haga, Yoshinori; Yamamoto, Etsuji; Onuki, Yoshichika

2007-01-01

We have observed the band structure and Fermi surfaces of the heavy Fermion superconductor UPd 2 Al 3 by angle-resolved photoemission experiments in the soft X-ray region. We observed renormalized quasi-particle bands in the vicinity of the Fermi level and strongly dispersive bands on the higher binding energy side. Our observation suggests that the structure previously assigned to contributions from localized states in the U 5f spectrum has strong energy dispersions

Theoretical study of the femtosecond-resolved photoelectron spectrum of the NO molecule

International Nuclear Information System (INIS)

Meng Qingtian; Yang Guanghui; Sun Hailin; Han Keli; Lou Nanquan

2003-01-01

The effect of laser fields on the NO interaction potentials is obtained by the calculation of time-resolved photoelectron spectrum (TRPES) using the time-dependent wave-packet method. The calculation not only shows that the overlap of the pump-probe pulses makes some NO molecular 'invisible' states visible, but also that the coupling strength and the positions of relevant curves change on increasing the laser intensity. These changed potentials affect their dynamical behavior and influence the shape and position of each peak in TRPES. That the coupling strength of relevant potentials can be changed by the field-matter interaction is consistent with our ab initio calculations

Introduction to Time-Resolved Spectroscopy: Nanosecond Transient Absorption and Time-Resolved Fluorescence of Eosin B

Science.gov (United States)

Farr, Erik P.; Quintana, Jason C.; Reynoso, Vanessa; Ruberry, Josiah D.; Shin, Wook R.; Swartz, Kevin R.

2018-01-01

Here we present a new undergraduate laboratory that will introduce the concepts of time-resolved spectroscopy and provide insight into the natural time scales on which chemical dynamics occur through direct measurement. A quantitative treatment of the acquired data will provide a deeper understanding of the role of quantum mechanics and various…

20 CFR 404.1694 - Final accounting by the State.

Science.gov (United States)

2010-04-01

... function. Disputes concerning final accounting issues which cannot be resolved between the State and us... 20 Employees' Benefits 2 2010-04-01 2010-04-01 false Final accounting by the State. 404.1694... DISABILITY INSURANCE (1950- ) Determinations of Disability Assumption of Disability Determination Function...

20 CFR 416.1094 - Final accounting by the State.

Science.gov (United States)

2010-04-01

... function. Disputes concerning final accounting issues which cannot be resolved between the State and us... 20 Employees' Benefits 2 2010-04-01 2010-04-01 false Final accounting by the State. 416.1094... AGED, BLIND, AND DISABLED Determinations of Disability Assumption of Disability Determination Function...

Quantum Control of a Nitrogen-Vacancy Center using Surface Acoustic Waves in the Resolved Sideband Limit

Science.gov (United States)

Golter, David; Oo, Thein; Amezcua, Maira; Wang, Hailin

Micro-electromechanical systems research is producing increasingly sophisticated tools for nanophononic applications. Such technology is well-suited for achieving chip-based, integrated acoustic control of solid-state quantum systems. We demonstrate such acoustic control in an important solid-state qubit, the diamond nitrogen-vacancy (NV) center. Using an interdigitated transducer to generate a surface acoustic wave (SAW) field in a bulk diamond, we observe phonon-assisted sidebands in the optical excitation spectrum of a single NV center. This exploits the strong strain sensitivity of the NV excited states. The mechanical frequencies far exceed the relevant optical linewidths, reaching the resolved-sideband regime. This enables us to use the SAW field for driving Rabi oscillations on the phonon-assisted optical transition. These results stimulate the further integration of SAW-based technologies with the NV center system.

340 nm pulsed UV LED system for europium-based time-resolved fluorescence detection of immunoassays

OpenAIRE

Rodenko, Olga; Fodgaard, Henrik; Tidemand-Lichtenberg, Peter; Petersen, Paul Michael; Pedersen, Christian

2016-01-01

We report on the design, development and investigation of an optical system based on UV light emitting diode (LED) excitation at 340 nm for time-resolved fluorescence detection of immunoassays. The system was tested to measure cardiac marker Troponin I with a concentration of 200 ng/L in immunoassay. The signal-to-noise ratio was comparable to state-of-the-art Xenon flash lamp based unit with equal excitation energy and without overdriving the LED. We performed a comparative study of the flas...

Electronic structure of superconducting Bi2212 crystal by angle resolved ultra violet photoemission

International Nuclear Information System (INIS)

Saini, N.L.; Shrivastava, P.; Garg, K.B.

1993-01-01

The electronic structure of a high quality superconducting Bi 2 Sr 2 CaCu 2 Osub(8+δ) (Bi2212) single crystal is studied by angle resolved ultra violet photoemission (ARUPS) using He I (21.2 eV). Our results appear to show two bands crossing the Fermi level in ΓX direction of the Brillouin zone as reported by Takahashi et al. The bands at higher binding energy do not show any appreciable dispersion. The nature of the states near the Fermi level is discussed and the observed band structure is compared with the band structure calculations. (author)

Generalized Darcy–Oseen resolvent problem

Czech Academy of Sciences Publication Activity Database

Medková, Dagmar; Ptashnyk, M.; Varnhorn, W.

2016-01-01

Roč. 39, č. 6 (2016), s. 1621-1630 ISSN 0170-4214 Institutional support: RVO:67985840 Keywords : Darcy-Oseen resolvent problem * semipermeable membrane * Brinkman-Darcy equations * fluid flow between free-fluid domains and porous media Subject RIV: BA - General Mathematics Impact factor: 1.017, year: 2016 http://onlinelibrary.wiley.com/doi/10.1002/mma.3872/abstract

Time-resolved CT angiography in aortic dissection

International Nuclear Information System (INIS)

Meinel, Felix G.; Nikolaou, Konstantin; Weidenhagen, Rolf; Hellbach, Katharina; Helck, Andreas; Bamberg, Fabian; Reiser, Maximilian F.; Sommer, Wieland H.

2012-01-01

Objectives: We performed this study to assess feasibility and additional diagnostic value of time-resolved CT angiography of the entire aorta in patients with aortic dissection. Materials and methods: 14 consecutive patients with known or suspected aortic dissection (aged 60 ± 9 years) referred for aortic CT angiography were scanned on a dual-source CT scanner (Somatom Definition Flash; Siemens, Forchheim, Germany) using a shuttle mode for multiphasic image acquisition (range 48 cm, time resolution 6 s, 6 phases, 100 kV, 110 mAs/rot). Effective radiation doses were calculated from recorded dose length products. For all phases, CT densities were measured in the aortic lumen and renal parenchyma. From the multiphasic data, 3 phases corresponding to a triphasic standard CT protocol, served as a reference and were compared against findings from the time-resolved datasets. Results: Mean effective radiation dose was 27.7 ± 3.5 mSv. CT density of the true lumen peaked at 355 ± 53 HU. Compared to the simulated triphasic protocol, time-resolved CT angiography added diagnostic information regarding a number of important findings: the enhancement delay between true and false lumen (n = 14); the degree of membrane oscillation (n = 14); the perfusion delay in arteries originating from the false lumen (n = 9). Other additional information included true lumen collapse (n = 4), quantitative assessment of renal perfusion asymmetry (n = 2), and dynamic occlusion of aortic branches (n = 2). In 3/14 patients (21%), these additional findings of the multiphasic protocol altered patient management. Conclusions: Multiphasic, time-resolved CT angiography covering the entire aorta is feasible at a reasonable effective radiation dose and adds significant diagnostic information with therapeutic consequences in patients with aortic dissection.

Shallow nitrogen ion implantation: Evolution of chemical state and defect structure in titanium

Energy Technology Data Exchange (ETDEWEB)

Manojkumar, P.A., E-mail: manoj@igcar.gov.in [Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Chirayath, V.A.; Balamurugan, A.K.; Krishna, Nanda Gopala; Ilango, S.; Kamruddin, M.; Amarendra, G.; Tyagi, A.K. [Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Raj, Baldev [National Institute of Advanced Studies, Bangalore 560 012 (India)

2016-09-15

Highlights: • Low energy nitrogen ion implantation in titanium was studied. • Chemical and defect states were analyzed using SIMS, XPS and PAS. • SIMS and depth resolved XPS data showed good agreement. • Depth resolved defect and chemical states information were revealed. • Formation of 3 layers of defect states proposed to fit PAS results. - Abstract: Evolution of chemical states and defect structure in titanium during low energy nitrogen ion implantation by Plasma Immersion Ion Implantation (PIII) process is studied. The underlying process of chemical state evolution is investigated using secondary ion mass spectrometry and X-ray photoelectron spectroscopy. The implantation induced defect structure evolution as a function of dose is elucidated using variable energy positron annihilation Doppler broadening spectroscopy (PAS) and the results were corroborated with chemical state. Formation of 3 layers of defect state was modeled to fit PAS results.

Sequence-Dependent Mechanism of DNA Oligonucleotide Dehybridization Resolved through Infrared Spectroscopy.

Science.gov (United States)

Sanstead, Paul J; Stevenson, Paul; Tokmakoff, Andrei

2016-09-14

Despite its important role in biology and nanotechnology, many questions remain regarding the molecular mechanism and dynamics by which oligonucleotides recognize and hybridize to their complementary sequence. The thermodynamics and kinetics of DNA oligonucleotide hybridization and dehybridization are often assumed to involve an all-or-nothing two-state dissociation pathway, but deviations from this behavior can be considerable even for short sequences. We introduce a new strategy to characterize the base-pair-specific thermal dissociation mechanism of DNA oligonucleotides through steady-state and time-resolved infrared spectroscopy. Experiments are interpreted with a lattice model to provide a structure-specific interpretation. This method is applied to a model set of self-complementary 10-base-pair sequences in which the placement of GC base pairs is varied in an otherwise AT strand. Through a combination of Fourier transform infrared and two-dimensional infrared spectroscopy, experiments reveal varying degrees of deviation from simple two-state behavior. As the temperature is increased, duplexes dissociate through a path in which the terminal bases fray, without any significant contribution from loop configurations. Transient temperature jump experiments reveal time scales of 70-100 ns for fraying and 10-30 μs for complete dissociation near the melting temperature. Whether or not frayed states are metastable intermediates or short-lived configurations during the full dissociation of the duplex is dictated by the nucleobase sequence.

An ultrafast angle-resolved photoemission apparatus for measuring complex materials

International Nuclear Information System (INIS)

Smallwood, Christopher L.; Lanzara, Alessandra; Jozwiak, Christopher; Zhang Wentao

2012-01-01

We present technical specifications for a high resolution time- and angle-resolved photoemission spectroscopy setup based on a hemispherical electron analyzer and cavity-dumped solid state Ti:sapphire laser used to generate pump and probe beams, respectively, at 1.48 and 5.93 eV. The pulse repetition rate can be tuned from 209 Hz to 54.3 MHz. Under typical operating settings the system has an overall energy resolution of 23 meV, an overall momentum resolution of 0.003 Å −1 , and an overall time resolution of 310 fs. We illustrate the system capabilities with representative data on the cuprate superconductor Bi 2 Sr 2 CaCu 2 O 8+δ . The descriptions and analyses presented here will inform new developments in ultrafast electron spectroscopy.

Pump-dump-probe and pump-repump-probe ultrafast spectroscopy resolves cross section of an early ground state intermediate and stimulated emission in the photoreactions of the Pr ground state of the cyanobacterial phytochrome Cph1.

Science.gov (United States)

Fitzpatrick, Ann E; Lincoln, Craig N; van Wilderen, Luuk J G W; van Thor, Jasper J

2012-01-26

contrast, using a 680 nm dump pulse, ground state formation is observed for all models examined. The ΔΔOD signals were dominated by stimulated emission, at both 1 and 14 ps delays for the longer wavelength excitation. The GSI, which is revealed by the PRP measurements and not resolved from pump-probe measurements, is found to be directly formed from the excited state of Pr, and its formation is considered using heterogeneous, homogeneous, and target models to globally fit the data.

Distortion dependent intersystem crossing: A femtosecond time-resolved photoelectron spectroscopy study of benzene, toluene, and p-xylene

Directory of Open Access Journals (Sweden)

Anne B. Stephansen

2017-07-01

Full Text Available The competition between ultrafast intersystem crossing and internal conversion in benzene, toluene, and p-xylene is investigated with time-resolved photoelectron spectroscopy and quantum chemical calculations. By exciting to S2 out-of-plane symmetry breaking, distortions are activated at early times whereupon spin-forbidden intersystem crossing becomes (partly allowed. Natural bond orbital analysis suggests that the pinnacle carbon atoms distorting from the aromatic plane change hybridization between the planar Franck-Condon geometry and the deformed (boat-shaped S2 equilibrium geometry. The effect is observed to increase in the presence of methyl-groups on the pinnacle carbon-atoms, where largest extents of σ and π orbital-mixing are observed. This is fully consistent with the time-resolved spectroscopy data: Toluene and p-xylene show evidence for ultrafast triplet formation competing with internal conversion, while benzene appears to only decay via internal conversion within the singlet manifold. For toluene and p-xylene, internal conversion to S1 and intersystem crossing to T3 occur within the time-resolution of our instrument. The receiver triplet state (T3 is found to undergo internal conversion in the triplet manifold within ≈100–150 fs (toluene or ≈180–200 fs (p-xylene as demonstrated by matching rise and decay components of upper and lower triplet states. Overall, the effect of methylation is found to both increase the intersystem crossing probability and direct the molecular axis of the excited state dynamics.

Mapping of trap densities and hotspots in pentacene thin-film transistors by frequency-resolved scanning photoresponse microscopy.

Science.gov (United States)

Westermeier, Christian; Fiebig, Matthias; Nickel, Bert

2013-10-25

Frequency-resolved scanning photoresponse microscopy of pentacene thin-film transistors is reported. The photoresponse pattern maps the in-plane distribution of trap states which is superimposed by the level of trap filling adjusted by the gate voltage of the transistor. Local hotspots in the photoresponse map thus indicate areas of high trap densities within the pentacene thin film. © 2013 WILEY-VCH Verlag GmbH 8 Co. KGaA, Weinheim.

Butterfly Deformation Modes in a Photoexcited Pyrazolate-Bridged Pt Complex Measured by Time-Resolved X-Ray Scattering in Solution

DEFF Research Database (Denmark)

Haldrup, Kristoffer; Dohn, Asmus Ougaard; Shelby, Megan L.

2016-01-01

the monochromatic X-ray pulses at Beamline 11IDD of the Advanced Photon Source. The excited-state structural analysis of 1 was performed based on the results from both transient WAXS measurements and density functional theory calculations to shed light on the primary structural changes in its triplet metal-metal...... excited state has remained scarce. Using time-resolved wide-angle X-ray scattering (WAXS), the excited triplet state molecular structure of [Pt(ppy)(μ-t-Bu2pz)]2 (ppy = 2-phenylpyridine; t-Bu2pz = 3,5-di-tert-butylpyrazolate), complex 1, was obtained in a dilute (0.5 mM) toluene solution utilizing...

Reverse Universal Resolving Algorithm and inverse driving

DEFF Research Database (Denmark)

Pécseli, Thomas

2012-01-01

Inverse interpretation is a semantics based, non-standard interpretation of programs. Given a program and a value, an inverse interpreter finds all or one of the inputs, that would yield the given value as output with normal forward evaluation. The Reverse Universal Resolving Algorithm is a new...... variant of the Universal Resolving Algorithm for inverse interpretation. The new variant outperforms the original algorithm in several cases, e.g., when unpacking a list using inverse interpretation of a pack program. It uses inverse driving as its main technique, which has not been described in detail...... before. Inverse driving may find application with, e.g., supercompilation, thus suggesting a new kind of program inverter....