Abnormal sleep/wake dynamics in orexin knockout mice.

PubMed

Diniz Behn, Cecilia G; Klerman, Elizabeth B; Mochizuki, Takatoshi; Lin, Shih-Chieh; Scammell, Thomas E

2010-03-01

Narcolepsy with cataplexy is caused by a loss of orexin (hypocretin) signaling, but the physiologic mechanisms that result in poor maintenance of wakefulness and fragmented sleep remain unknown. Conventional scoring of sleep cannot reveal much about the process of transitioning between states or the variations within states. We developed an EEG spectral analysis technique to determine whether the state instability in a mouse model of narcolepsy reflects abnormal sleep or wake states, faster movements between states, or abnormal transitions between states. We analyzed sleep recordings in orexin knockout (OXKO) mice and wild type (WT) littermates using a state space analysis technique. This non-categorical approach allows quantitative and unbiased examination of sleep/wake states and state transitions. OXKO mice spent less time in deep, delta-rich NREM sleep and in active, theta-rich wake and instead spent more time near the transition zones between states. In addition, while in the midst of what should be stable wake, OXKO mice initiated rapid changes into NREM sleep with high velocities normally seen only in transition regions. Consequently, state transitions were much more frequent and rapid even though the EEG progressions during state transitions were normal. State space analysis enables visualization of the boundaries between sleep and wake and shows that narcoleptic mice have less distinct and more labile states of sleep and wakefulness. These observations provide new perspectives on the abnormal state dynamics resulting from disrupted orexin signaling and highlight the usefulness of state space analysis in understanding narcolepsy and other sleep disorders.

Transitions to Synchrony in Coupled Bursting Neurons

NASA Astrophysics Data System (ADS)

Dhamala, Mukeshwar; Jirsa, Viktor K.; Ding, Mingzhou

2004-01-01

Certain cells in the brain, for example, thalamic neurons during sleep, show spike-burst activity. We study such spike-burst neural activity and the transitions to a synchronized state using a model of coupled bursting neurons. In an electrically coupled network, we show that the increase of coupling strength increases incoherence first and then induces two different transitions to synchronized states, one associated with bursts and the other with spikes. These sequential transitions to synchronized states are determined by the zero crossings of the maximum transverse Lyapunov exponents. These results suggest that synchronization of spike-burst activity is a multi-time-scale phenomenon and burst synchrony is a precursor to spike synchrony.

Accuracy of maximum likelihood estimates of a two-state model in single-molecule FRET

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gopich, Irina V.

2015-01-21

Photon sequences from single-molecule Förster resonance energy transfer (FRET) experiments can be analyzed using a maximum likelihood method. Parameters of the underlying kinetic model (FRET efficiencies of the states and transition rates between conformational states) are obtained by maximizing the appropriate likelihood function. In addition, the errors (uncertainties) of the extracted parameters can be obtained from the curvature of the likelihood function at the maximum. We study the standard deviations of the parameters of a two-state model obtained from photon sequences with recorded colors and arrival times. The standard deviations can be obtained analytically in a special case when themore » FRET efficiencies of the states are 0 and 1 and in the limiting cases of fast and slow conformational dynamics. These results are compared with the results of numerical simulations. The accuracy and, therefore, the ability to predict model parameters depend on how fast the transition rates are compared to the photon count rate. In the limit of slow transitions, the key parameters that determine the accuracy are the number of transitions between the states and the number of independent photon sequences. In the fast transition limit, the accuracy is determined by the small fraction of photons that are correlated with their neighbors. The relative standard deviation of the relaxation rate has a “chevron” shape as a function of the transition rate in the log-log scale. The location of the minimum of this function dramatically depends on how well the FRET efficiencies of the states are separated.« less

Accuracy of maximum likelihood estimates of a two-state model in single-molecule FRET

PubMed Central

Gopich, Irina V.

2015-01-01

Photon sequences from single-molecule Förster resonance energy transfer (FRET) experiments can be analyzed using a maximum likelihood method. Parameters of the underlying kinetic model (FRET efficiencies of the states and transition rates between conformational states) are obtained by maximizing the appropriate likelihood function. In addition, the errors (uncertainties) of the extracted parameters can be obtained from the curvature of the likelihood function at the maximum. We study the standard deviations of the parameters of a two-state model obtained from photon sequences with recorded colors and arrival times. The standard deviations can be obtained analytically in a special case when the FRET efficiencies of the states are 0 and 1 and in the limiting cases of fast and slow conformational dynamics. These results are compared with the results of numerical simulations. The accuracy and, therefore, the ability to predict model parameters depend on how fast the transition rates are compared to the photon count rate. In the limit of slow transitions, the key parameters that determine the accuracy are the number of transitions between the states and the number of independent photon sequences. In the fast transition limit, the accuracy is determined by the small fraction of photons that are correlated with their neighbors. The relative standard deviation of the relaxation rate has a “chevron” shape as a function of the transition rate in the log-log scale. The location of the minimum of this function dramatically depends on how well the FRET efficiencies of the states are separated. PMID:25612692

Determining the transition-state structure for different SN2 reactions using experimental nucleophile carbon and secondary alpha-deuterium kinetic isotope effects and theory.

PubMed

Westaway, Kenneth C; Fang, Yao-ren; MacMillar, Susanna; Matsson, Olle; Poirier, Raymond A; Islam, Shahidul M

2008-10-16

Nucleophile (11)C/ (14)C [ k (11)/ k (14)] and secondary alpha-deuterium [( k H/ k D) alpha] kinetic isotope effects (KIEs) were measured for the S N2 reactions between tetrabutylammonium cyanide and ethyl iodide, bromide, chloride, and tosylate in anhydrous DMSO at 20 degrees C to determine whether these isotope effects can be used to determine the structure of S N2 transition states. Interpreting the experimental KIEs in the usual fashion (i.e., that a smaller nucleophile KIE indicates the Nu-C alpha transition state bond is shorter and a smaller ( k H/ k D) alpha is found when the Nu-LG distance in the transition state is shorter) suggests that the transition state is tighter with a slightly shorter NC-C alpha bond and a much shorter C alpha-LG bond when the substrate has a poorer halogen leaving group. Theoretical calculations at the B3LYP/aug-cc-pVDZ level of theory support this conclusion. The results show that the experimental nucleophile (11)C/ (14)C KIEs can be used to determine transition-state structure in different reactions and that the usual method of interpreting these KIEs is correct. The magnitude of the experimental secondary alpha-deuterium KIE is related to the nucleophile-leaving group distance in the S N2 transition state ( R TS) for reactions with a halogen leaving group. Unfortunately, the calculated and experimental ( k H/ k D) alpha's change oppositely with leaving group ability. However, the calculated ( k H/ k D) alpha's duplicate both the trend in the KIE with leaving group ability and the magnitude of the ( k H/ k D) alpha's for the ethyl halide reactions when different scale factors are used for the high and the low energy vibrations. This suggests it is critical that different scaling factors for the low and high energy vibrations be used if one wishes to duplicate experimental ( k H/ k D) alpha's. Finally, neither the experimental nor the theoretical secondary alpha-deuterium KIEs for the ethyl tosylate reaction fit the trend found for the reactions with a halogen leaving group. This presumably is found because of the bulky (sterically hindered) leaving group in the tosylate reaction. From every prospective, the tosylate reaction is too different from the halogen reactions to be compared.

Computer program for determining rotational line intensity factors for diatomic molecules

NASA Technical Reports Server (NTRS)

Whiting, E. E.

1973-01-01

A FORTRAN IV computer program, that provides a new research tool for determining reliable rotational line intensity factors (also known as Honl-London factors), for most electric and magnetic dipole allowed diatomic transitions, is described in detail. This users manual includes instructions for preparing the input data, a program listing, detailed flow charts, and three sample cases. The program is applicable to spin-allowed dipole transitions with either or both states intermediate between Hund's case (a) and Hund's case (b) coupling and to spin-forbidden dipole transitions with either or both states intermediate between Hund's case (c) and Hund's case (b) coupling.

Theoretical analysis of Lumry-Eyring models in differential scanning calorimetry

PubMed Central

Sanchez-Ruiz, Jose M.

1992-01-01

A theoretical analysis of several protein denaturation models (Lumry-Eyring models) that include a rate-limited step leading to an irreversibly denatured state of the protein (the final state) has been carried out. The differential scanning calorimetry transitions predicted for these models can be broadly classified into four groups: situations A, B, C, and C′. (A) The transition is calorimetrically irreversible but the rate-limited, irreversible step takes place with significant rate only at temperatures slightly above those corresponding to the transition. Equilibrium thermodynamics analysis is permissible. (B) The transition is distorted by the occurrence of the rate-limited step; nevertheless, it contains thermodynamic information about the reversible unfolding of the protein, which could be obtained upon the appropriate data treatment. (C) The heat absorption is entirely determined by the kinetics of formation of the final state and no thermodynamic information can be extracted from the calorimetric transition; the rate-determining step is the irreversible process itself. (C′) same as C, but, in this case, the rate-determining step is a previous step in the unfolding pathway. It is shown that ligand and protein concentration effects on transitions corresponding to situation C (strongly rate-limited transitions) are similar to those predicted by equilibrium thermodynamics for simple reversible unfolding models. It has been widely held in recent literature that experimentally observed ligand and protein concentration effects support the applicability of equilibrium thermodynamics to irreversible protein denaturation. The theoretical analysis reported here disfavors this claim. PMID:19431826

76 FR 61135 - Waiver of Restriction on Assistance to the Transitional Federal Government of Somalia

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-03

... DEPARTMENT OF STATE [Public Notice: 7627] Waiver of Restriction on Assistance to the Transitional Federal Government of Somalia Pursuant to Section 7086(c)(2) of the Department of State, Foreign... Somalia and I hereby waive such restriction. This determination shall be reported to the Congress, and...

Transit profiles : the thirty largest agencies for the 1995 National Transit Database report year

DOT National Transportation Integrated Search

1996-01-01

This publication consists of consolidated profiles for the thirty (30) largest transit agencies in the United States for the 1995 Report Year, with the fiscal years ending during the 1995 calendar year. The criterion for determining the largest trans...

Characterizing longitudinal health state transitions among heroin, cocaine, and methamphetamine users

PubMed Central

Nosyk, B; Li, L; Evans, E; Huang, D; Min, J; Kerr, T; Brecht, ML; Hser, YI

2014-01-01

Aims Characterize longitudinal patterns of drug use careers and identify determinants of drug use frequency across cohorts of primary heroin, methamphetamine (MA) and cocaine users. Design Pooled analysis of prospective cohort studies. Settings Illicit drug users recruited from community, criminal justice and drug treatment settings in California, USA. Participants We used longitudinal data on from five observational cohort studies featuring primary users of heroin (N=629), cocaine (N=694) and methamphetamine (N=474). The mean duration of follow-up was 20.9 years. Measurements Monthly longitudinal data was arranged according to five health states (incarceration, drug treatment, abstinence, non-daily and daily use). We fitted proportional hazards (PH) frailty models to determine independent differences in successive episode durations. We then executed multi-state Markov (MSM) models to estimate probabilities of transitioning between health states, and the determinants of these transitions. Findings Across primary drug use types, PH frailty models demonstrated durations of daily use diminished in successive episodes over time. MSM models revealed primary stimulant users had more erratic longitudinal patterns of drug use, transitioning more rapidly between periods of treatment, abstinence, non-daily and daily use. MA users exhibited relatively longer durations of high-frequency use. Criminal engagement had a destabilizing effect on health state durations across drug types. Longer incarceration histories were associated with delayed transitions towards cessation. Conclusions PH frailty and MSM modeling techniques provided complementary information on longitudinal patterns of drug abuse. This information can inform clinical practice and policy, and otherwise be used in health economic simulation models, designed to inform resource allocation decisions. PMID:24837584

Electronic transitions of tantalum monofluoride

NASA Astrophysics Data System (ADS)

Ng, K. F.; Zou, Wenli; Liu, Wenjian; Cheung, A. S.-C.

2017-03-01

The electronic transition spectrum of the tantalum monofluoride (TaF) molecule in the spectral region between 448 and 560 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. The TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Twenty-two vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transitions. The X3Σ-(0+) state has been identified to be the ground state and the determined equilibrium bond length, re, and vibrational frequency, ωe, are 1.8184 Å and 700.1 cm-1, respectively. The low-lying Λ-S states and Ω sub-states of TaF were also theoretically studied at the MRCISD+Q level of theory with spin-orbit coupling. The Ω = 0+ and 2 sub-states from the -3Σ and 3Φ state have been found to be the ground and the first excited states, respectively, which agrees well with our experimental determinations. This work represents the first experimental investigation of the molecular structure of the TaF molecule.

Ionic and Covalent Stabilization of Intermediates and Transition States in Catalysis by Solid Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deshlahra, Prashant; Carr, Robert T.; Iglesia, Enrique

Reactivity descriptors describe catalyst properties that determine the stability of kinetically relevant transition states and adsorbed intermediates. Theoretical descriptors, such as deprotonation energies (DPE), rigorously account for Brønsted acid strength for catalytic solids with known structure. Here, mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate (POM) clusters and gaseous mineral acids. Turnover rates are lower and kinetically relevant species are less stable on Mo than W POMmore » clusters with similar acid strength, and such species are more stable on mineral acids than that predicted from W-POM DPE–reactivity trends, indicating that DPE and acid strength are essential but incomplete reactivity descriptors. Born–Haber thermochemical cycles indicate that these differences reflect more effective charge reorganization upon deprotonation of Mo than W POM clusters and the much weaker reorganization in mineral acids. Such covalency is disrupted upon deprotonation but cannot be recovered fully upon formation of ion pairs at transition states. Predictive descriptors of reactivity for general classes of acids thus require separate assessments of the covalent and ionic DPE components. Here, we describe methods to estimate electrostatic interactions, which, taken together with energies derived from density functional theory, give the covalent and ionic energy components of protons, intermediates, and transition states. In doing so, we provide a framework to predict the reactive properties of protons for chemical reactions mediated by ion-pair transition states.« less

A molecular symmetry analysis of the electronic states and transition dipole moments for molecules with two torsional degrees of freedom

DOE Office of Scientific and Technical Information (OSTI.GOV)

Obaid, R.; Applied Chemistry Department, Palestine Polytechnic University, Hebron, Palestine; Leibscher, M., E-mail: monika.leibscher@itp.uni-hannover.de

2015-02-14

We present a molecular symmetry analysis of electronic states and transition dipole moments for molecules which undergo large amplitude intramolecular torsions. The method is based on the correlation between the point group of the molecule at highly symmetric configurations and the molecular symmetry group. As an example, we determine the global irreducible representations of the electronic states and transition dipole moments for the quinodimethane derivative 2-[4-(cyclopenta-2,4-dien-1-ylidene)cyclohexa-2,5-dien-1-ylidene]-2H-1, 3-dioxole for which two torsional degrees of freedom can be activated upon photo-excitation and construct the resulting symmetry adapted transition dipole functions.

An algorithm for minimum-cost set-point ordering in a cryogenic wind tunnel

NASA Technical Reports Server (NTRS)

Tripp, J. S.

1981-01-01

An algorithm for minimum cost ordering of set points in a cryogenic wind tunnel is developed. The procedure generates a matrix of dynamic state transition costs, which is evaluated by means of a single-volume lumped model of the cryogenic wind tunnel and the use of some idealized minimum-costs, which is evaluated by means of a single-volume lumped model of the cryogenic wind tunnel and the use of some idealized minimum-cost state-transition control strategies. A branch and bound algorithm is employed to determine the least costly sequence of state transitions from the transition-cost matrix. Some numerical results based on data for the National Transonic Facility are presented which show a strong preference for state transitions that consume to coolant. Results also show that the choice of the terminal set point in an open odering can produce a wide variation in total cost.

Enhancing transit polio vaccination in collaboration with targeted stakeholders in Kaduna State, Nigeria: Lessons learnt: 2014-2015.

PubMed

Musa, Audu; Abba, Bashir; Ningi, Adamu M I; Gali, Emanuel; Bawa, Samuel; Manneh, Fadninding; Mkanda, Pascal; Banda, Richard; Yehuluashet, Yared G; Tegegne, Sisay G; Umeh, Gregory; Nsubuga, Peter; Etsano, Andrew; Shuaib, Faisal; Mohammed, Ado; Vaz, Rui G

2016-10-10

In Kaduna State of Nigeria, the high influx of people from neighboring states with eligible children for polio vaccination represents a significant proportion of the target population. Many of these children are often missed by the vaccination team. The purpose of the study was to determine the contribution of targeted stakeholders in transit polio vaccination. We used the trends of vaccinated children at transit points, motor parks and markets, well as total children vaccinated by transit teams in Chikun, Igabi and Sabon Gari Local Government Areas (LGAs) of Kaduna State, Nigeria, four rounds before and after the introduction of transit polio vaccination with targeted stakeholders in Kaduna State. A total of 87,502 under-5 children were vaccinated by the various transit teams in the three LGAs, which accounted for 3.2% of the total 2,781,162 children vaccinated by the three LGAs. For transit point vaccination, the number of vaccinated children increased from 1026 to 19,289 (302%), while motor park vaccination increased from 1289 to 4106 (318%) and market vaccination increased from 10,488 to 14,511 (138%), four rounds after the introduction of transit polio vaccination with targeted stakeholders. Engagement of targeted stakeholders significantly enhanced transit polio vaccination in Kaduna State, Nigeria. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Phase separation and second-order phase transition in the phenomenological model for a Coulomb-frustrated two-dimensional system

NASA Astrophysics Data System (ADS)

Mamin, R. F.; Shaposhnikova, T. S.; Kabanov, V. V.

2018-03-01

We have considered the model of the phase transition of the second order for the Coulomb frustrated 2D charged system. The coupling of the order parameter with the charge was considered as the local temperature. We have found that in such a system, an appearance of the phase-separated state is possible. By numerical simulation, we have obtained different types ("stripes," "rings," "snakes") of phase-separated states and determined the parameter ranges for these states. Thus the system undergoes a series of phase transitions when the temperature decreases. First, the system moves from the homogeneous state with a zero order parameter to the phase-separated state with two phases in one of which the order parameter is zero and, in the other, it is nonzero (τ >0 ). Then a first-order transition occurs to another phase-separated state, in which both phases have different and nonzero values of the order parameter (for τ <0 ). Only a further decrease of temperature leads to a transition to a homogeneous ordered state.

OPTICAL ABSORPTION SPECTRUM OF ANTIFERROMAGNETIC MNF2.

DTIC Science & Technology

separated in energy and easily identifiable, (3) has a very simple ground state, and (4) has a well studied magnon structure, an investigation was...undertaken of the excited states in the hope of observing other magnetic dipole transitions and their accompanying magnon sidebands. This study was...similarities between the magnon sidebands in several excited states of the Mn(+2) ion, and to determine the importance of spin assisted transitions in

76 FR 60112 - Culturally Significant Objects Imported for Exhibition Determinations: “Byzantium and Islam: Age...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-28

... DEPARTMENT OF STATE [Public Notice 7615] Culturally Significant Objects Imported for Exhibition Determinations: ``Byzantium and Islam: Age of Transition (7th-9th Century)'' SUMMARY: Notice is hereby given of... included in the exhibition ``Byzantium and Islam: Age of Transition (7th-9th Century),'' imported from...

Electron Scattering from MERCURY-198 and Mercury -204.

NASA Astrophysics Data System (ADS)

Laksanaboonsong, Jarungsaeng

This experiment is the first electron scattering study on mercury isotopes. Electron scattering from ^{198}Hg and ^{204 }Hg has been performed at the NIKHEF-K Medium Energy Accelerator. Measured cross sections cover an effective momentum transfer range from 0.4 to 2.9 fm^ {-1}. Elastic cross sections were determined for scattering from both isotopes. Cross section for inelastic excitations in ^{198}Hg below 3 MeV were also determined. Measured cross sections were fit using DWBA phase shift codes to determine coefficients for Fourier-Bessel expansions of ground state and transition charge densities. Differences between the ground state charge densities of the two isotopes reveal the effect of the polarization of the proton core in response to the addition of neutrons. Spin and parity of several excited states of ^{198}Hg were determined. Extracted transition densities of these states show their predominantly collective nature. Charge densities for members of the ground state rotational band were compared with axially symmetric Hartree-Fock and geometrical model predictions.

Electric Monopole Transition Strengths in the Stable Nickel Isotopes

NASA Astrophysics Data System (ADS)

Evitts, Lee John

A series of measurements of stable nickel isotopes were performed at the Australian National University in Canberra. Excited states in 58,60,62Ni were populated via inelastic scattering of proton beams delivered by the 14UD Pelletron accelerator. Multiple setups were used in order to determine the structure of low-lying states. The CAESAR array of Compton-suppressed HPGe detectors was used to measure the (E2/M1) mixing ratio of transitions from angular distributions of gamma rays. The Super-e spectrometer was used to measure conversion coefficients for a number of J to J transitions. The data obtained from both devices was combined with previously measured parent lifetimes and branching ratios to determine E0 transition strengths between J-pi transitions. The E0 transition strength for the second 0+ to first 0+ transitions in 60,62Ni have been measured for the first time through internal conversion electron detection. The experimental value of 132(+59,-70) for 62Ni agrees within 2 sigma of the previous result obtained from internal pair formation. However it is likely that the previous experimental results used an outdated theoretical model for internal pair formation emission. This work also represents the first measurements of E0 transition strengths between 2+ states in Ni isotopes. There is generally large E0 strength between the 2+ states, particularly in the second 2+ to first 2+ transition, however there is also a large uncertainty in the measurements owing to the difficulties involved in measuring conversion coefficients. In 62Ni, the E0 transition strength of 172(+62,-77) for the second 2+ to first 2+ transition gives further weight to the argument against the spherical vibrator model, as an E0 transition is forbidden if there is a change of only one phonon. The large measurement also indicates the presence of shape coexistence, complementing the recent experimental work carried out in the neutron-rich Ni isotopes.

Determination of Insulator-to-Semiconductor Transition in Sol-Gel Oxide Semiconductors Using Derivative Spectroscopy.

PubMed

Lee, Woobin; Choi, Seungbeom; Kim, Kyung Tae; Kang, Jingu; Park, Sung Kyu; Kim, Yong-Hoon

2015-12-23

We report a derivative spectroscopic method for determining insulator-to-semiconductor transition during sol-gel metal-oxide semiconductor formation. When an as-spun sol-gel precursor film is photochemically activated and changes to semiconducting state, the light absorption characteristics of the metal-oxide film is considerable changed particularly in the ultraviolet region. As a result, a peak is generated in the first-order derivatives of light absorption ( A' ) vs. wavelength (λ) plots, and by tracing the peak center shift and peak intensity, transition from insulating-to-semiconducting state of the film can be monitored. The peak generation and peak center shift are described based on photon-energy-dependent absorption coefficient of metal-oxide films. We discuss detailed analysis method for metal-oxide semiconductor films and its application in thin-film transistor fabrication. We believe this derivative spectroscopy based determination can be beneficial for a non-destructive and a rapid monitoring of the insulator-to-semiconductor transition in sol-gel oxide semiconductor formation.

Diels–Alder Reactions of Allene with Benzene and Butadiene: Concerted, Stepwise, and Ambimodal Transition States

PubMed Central

2015-01-01

Multiconfigurational complete active space methods (CASSCF and CASPT2) have been used to investigate the (4 + 2) cycloadditions of allene with butadiene and with benzene. Both concerted and stepwise radical pathways were examined to determine the mechanism of the Diels–Alder reactions with an allene dienophile. Reaction with butadiene occurs via a single ambimodal transition state that can lead to either the concerted or stepwise trajectories along the potential energy surface, while reaction with benzene involves two separate transition states and favors the concerted mechanism relative to the stepwise mechanism via a diradical intermediate. PMID:25216056

Localized Ignition And Subsequent Flame Spread Over Solid Fuels In Microgravity

NASA Technical Reports Server (NTRS)

Kashiwagi, T.; Nakamura, Y.; Prasad, K.; Baum, H.; Olson, S.; Fujita, O.; Nishizawa, K.; Ito, K.

2003-01-01

Localized ignition is initiated by an external radiant source at the middle of a thin solid sheet under external slow flow, simulating fire initiation in a spacecraft with a slow ventilation flow. Ignition behavior, subsequent transition simultaneously to upstream and downstream flame spread, and flame growth behavior are studied theoretically and experimentally. There are two transition stages in this study; one is the first transition from the onset of the ignition to form an initial anchored flame close to the sample surface, near the ignited area. The second transition is the flame growth stage from the anchored flame to a steady fire spread state (i.e. no change in flame size or in heat release rate) or a quasi-steady state, if either exists. Observations of experimental spot ignition characteristics and of the second transition over a thermally thin paper were made to determine the effects of external flow velocity. Both transitions have been studied theoretically to determine the effects of the confinement by a relatively small test chamber, of the ignition configuration (ignition across the sample width vs spot ignition), and of the external flow velocity on the two transitions over a thermally thin paper. This study is currently extending to two new areas; one is to include a thermoplastic sample such poly(methymethacrylate), PMMA, and the other is to determine the effects of sample thickness on the transitions. The recent results of these new studies on the first transition are briefly reported.

Thickness-dependent phase transition in graphite under high magnetic field

NASA Astrophysics Data System (ADS)

Taen, Toshihiro; Uchida, Kazuhito; Osada, Toshihito

2018-03-01

Various electronic phases emerge when applying high magnetic fields in graphite. However, the origin of a semimetal-insulator transition at B ≃30 T is still not clear, while an exotic density-wave state is theoretically proposed. In order to identify the electronic state of the insulator phase, we investigate the phase transition in thin-film graphite samples that were fabricated on silicon substrate by a mechanical exfoliation method. The critical magnetic fields of the semimetal-insulator transition in thin-film graphite shift to higher magnetic fields, accompanied by a reduction in temperature dependence. These results can be qualitatively reproduced by a density-wave model by introducing a quantum size effect. Our findings establish the electronic state of the insulator phase as a density-wave state standing along the out-of-plane direction, and help determine the electronic states in other high-magnetic-field phases.

Potential Energy Curves, Transition Dipole Moments, and Franck-Condon Factors of the 12 Low-Lying States of BrO- Anion.

PubMed

Yin, Yuan; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue

2017-11-02

This work investigates the spectroscopic parameters, vibrational levels, and transition probabilities of 12 low-lying states, which are generated from the first dissociation limit, Br( 2 P u ) + O - ( 2 P u ), of the BrO - anion. The 12 states are X 1 Σ + , 2 1 Σ + , 1 1 Σ - , 1 1 Π, 2 1 Π, 1 1 Δ, a 3 Π, 1 3 Σ + , 2 3 Σ + , 1 3 Σ - , 2 3 Π, and 1 3 Δ. The potential energy curves are calculated with the complete active-space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with Davidson modification. The dissociation energy D 0 of X 1 Σ + state is determined to be approximately 26876.44 cm -1 , which agrees well with the experimental one of 26494.50 cm -1 . Of these 12 states, the 2 1 Σ + , 1 1 Σ - , 2 1 Π, 1 1 Δ, 1 3 Σ + , 2 3 Σ + , 2 3 Π, and 1 3 Δ states are very weakly bound states, whose well depths are only several-hundred cm -1 . The a 3 Π, 2 3 Π, and 1 3 Δ states are inverted and account for the spin-orbit coupling effect. No states are repulsive regardless of whether the spin-orbit coupling effect is included. The spectroscopic parameters and vibrational levels are determined. The transition dipole moments of 12-pair electronic states are calculated. Franck-Condon factors of a number of transitions of more than 20-pair electronic states are evaluated. The electronic transitions are discussed. The spin-orbit coupling effect on the spectroscopic parameters and vibrational properties is profound for all the states except for X 1 Σ + , a 3 Π, and 1 1 Π. The spectroscopic parameters and transition probabilities obtained in this paper can provide some powerful guidelines for observing these states in a proper spectroscopy experiment, in particular the states that have very shallow potential wells.

Abnormal Sleep/Wake Dynamics in Orexin Knockout Mice

PubMed Central

Diniz Behn, Cecilia G.; Klerman, Elizabeth B.; Mochizuki, Takatoshi; Lin, Shih-Chieh; Scammell, Thomas E.

2010-01-01

Study Objectives: Narcolepsy with cataplexy is caused by a loss of orexin (hypocretin) signaling, but the physiologic mechanisms that result in poor maintenance of wakefulness and fragmented sleep remain unknown. Conventional scoring of sleep cannot reveal much about the process of transitioning between states or the variations within states. We developed an EEG spectral analysis technique to determine whether the state instability in a mouse model of narcolepsy reflects abnormal sleep or wake states, faster movements between states, or abnormal transitions between states. Design: We analyzed sleep recordings in orexin knockout (OXKO) mice and wild type (WT) littermates using a state space analysis technique. This non-categorical approach allows quantitative and unbiased examination of sleep/wake states and state transitions. Measurements and Results: OXKO mice spent less time in deep, delta-rich NREM sleep and in active, theta-rich wake and instead spent more time near the transition zones between states. In addition, while in the midst of what should be stable wake, OXKO mice initiated rapid changes into NREM sleep with high velocities normally seen only in transition regions. Consequently, state transitions were much more frequent and rapid even though the EEG progressions during state transitions were normal. Conclusions: State space analysis enables visualization of the boundaries between sleep and wake and shows that narcoleptic mice have less distinct and more labile states of sleep and wakefulness. These observations provide new perspectives on the abnormal state dynamics resulting from disrupted orexin signaling and highlight the usefulness of state space analysis in understanding narcolepsy and other sleep disorders. Citation: Diniz Behn CG; Klerman EB; Mochizuki T; Lin S; Scammell TE. Abnormal sleep/wake dynamics in orexin knockout mice. SLEEP 2010;33(3):297-306. PMID:20337187

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces.

PubMed

Crawford, Paul; Hu, P

2006-12-14

The dissociative adsorption of N2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Relativistic Coulomb excitation of 88Kr

NASA Astrophysics Data System (ADS)

Moschner, K.; Blazhev, A.; Jolie, J.; Warr, N.; Boutachkov, P.; Bednarczyk, P.; Sieja, K.; Algora, A.; Ameil, F.; Bentley, M. A.; Brambilla, S.; Braun, N.; Camera, F.; Cederkäll, J.; Corsi, A.; Danchev, M.; DiJulio, D.; Fahlander, C.; Gerl, J.; Giaz, A.; Golubev, P.; Górska, M.; Grebosz, J.; Habermann, T.; Hackstein, M.; Hoischen, R.; Kojouharov, I.; Kurz, N.; Mǎrginean, N.; Merchán, E.; Möller, T.; Naqvi, F.; Nara Singh, B. S.; Nociforo, C.; Pietralla, N.; Pietri, S.; Podolyák, Zs.; Prochazka, A.; Reese, M.; Reiter, P.; Rudigier, M.; Rudolph, D.; Sava, T.; Schaffner, H.; Scruton, L.; Taprogge, J.; Thomas, T.; Weick, H.; Wendt, A.; Wieland, O.; Wollersheim, H.-J.

2016-11-01

To investigate the systematics of mixed-symmetry states in N =52 isotones, a relativistic Coulomb excitation experiment was performed during the PreSPEC campaign at the GSI Helmholtzzentrum für Schwerionenforschung to determine E 2 transition strengths to 2+ states of the radioactive nucleus 88Kr. Absolute transition rates could be measured towards the first and third 2+ states. For the latter a mixed-symmetry character is suggested on the basis of the indication for a strong M 1 transition to the fully symmetric 21+ state, extending the knowledge of the N =52 isotones below Z =40 . A comparison with the proton-neutron interacting boson model and shell-model predictions is made and supports the assignment.

Local entanglement entropy of fermions as a marker of quantum phase transition in the one-dimensional Hubbard model

NASA Astrophysics Data System (ADS)

Cha, Min-Chul; Chung, Myung-Hoon

2018-05-01

We study quantum phase transition of interacting fermions by measuring the local entanglement entropy in the one-dimensional Hubbard model. The reduced density matrices for blocks of a few sites are constructed from the ground state wave function in infinite systems by adopting the matrix product state representation where time-evolving block decimations are performed to obtain the lowest energy states. The local entanglement entropy, constructed from the reduced density matrices, as a function of the chemical potential shows clear signatures of the Mott transition. The value of the central charge, numerically determined from the universal properties of the local entanglement entropy, confirms that the transition is caused by the suppression of the charge degrees of freedom.

Jet-cooled laser-induced fluorescence spectroscopy of cyclohexoxy: rotational and fine structure of molecules in nearly degenerate electronic States.

PubMed

Liu, Jinjun; Miller, Terry A

2014-12-26

The rotational structure of the previously observed B̃(2)A' ← X̃(2)A″ and B̃(2)A' ← Ã(2)A' laser-induced fluorescence spectra of jet-cooled cyclohexoxy radical (c-C6H11O) [ Zu, L.; Liu, J.; Tarczay, G.; Dupré, P; Miller, T. A. Jet-cooled laser spectroscopy of the cyclohexoxy radical. J. Chem. Phys. 2004 , 120 , 10579 ] has been analyzed and simulated using a spectroscopic model that includes the coupling between the nearly degenerate X̃ and à states separated by ΔE. The rotational and fine structure of these two states is reproduced by a 2-fold model using one set of molecular constants including rotational constants, spin-rotation constants (ε's), the Coriolis constant (Aζt), the quenched spin-orbit constant (aζed), and the vibronic energy separation between the two states (ΔE0). The energy level structure of both states can also be reproduced using an isolated-state asymmetric top model with rotational constants and effective spin-rotation constants (ε's) and without involving Coriolis and spin-orbit constants. However, the spin-orbit interaction introduces transitions that have no intensity using the isolated-state model but appear in the observed spectra. The line intensities are well simulated using the 2-fold model with an out-of-plane (b-) transition dipole moment for the B̃ ← X̃ transitions and in-plane (a and c) transition dipole moment for the B̃ ← à transitions, requiring the symmetry for the X̃ (Ã) state to be A″ (A'), which is consistent with a previous determination and opposite to that of isopropoxy, the smallest secondary alkoxy radical. The experimentally determined Ã-X̃ separation and the energy level ordering of these two states with different (A' and A″) symmetries are consistent with quantum chemical calculations. The 2-fold model also enables the independent determination of the two contributions to the Ã-X̃ separation: the relativistic spin-orbit interaction (magnetic effect) and the nonrelativistic vibronic separation between the lowest vibrational energy levels of these two states due to both electrostatic interaction (Coulombic effect) and difference in zero-point energies (kinetic effect).

Current signature sensor

NASA Technical Reports Server (NTRS)

Perotti, Jose M. (Inventor); Lucena, Angel (Inventor); Ihlefeld, Curtis (Inventor); Burns, Bradley (Inventor); Bassignani, Karin E. (Inventor)

2005-01-01

A solenoid health monitoring system uses a signal conditioner and controller assembly in one embodiment that includes analog circuitry and a DSP controller. The analog circuitry provides signal conditioning to the low-level raw signal coming from a signal acquisition assembly. Software running in a DSP analyzes the incoming data (recorded current signature) and determines the state of the solenoid whether it is energized, de-energized, or in a transitioning state. In one embodiment, the software identifies key features in the current signature during the transition phase and is able to determine the health of the solenoid.

Tuning stochastic transition rates in a bistable genetic network.

NASA Astrophysics Data System (ADS)

Chickarmane, Vijay; Peterson, Carsten

2009-03-01

We investigate the stochastic dynamics of a simple genetic network, a toggle switch, in which the system makes transitions between the two alternative states. Our interest is in exploring whether such stochastic transitions, which occur due to the intrinsic noise such as transcriptional and degradation events, can be slowed down/speeded up, without changing the mean expression levels of the two genes, which comprise the toggle network. Such tuning is achieved by linking a signaling network to the toggle switch. The signaling network comprises of a protein, which can exist either in an active (phosphorylated) or inactive (dephosphorylated) form, and where its state is determined by one of the genetic network components. The active form of the protein in turn feeds back on the dynamics of the genetic network. We find that the rate of stochastic transitions from one state to the other, is determined essentially by the speed of phosphorylation, and hence the rate can be modulated by varying the phosphatase levels. We hypothesize that such a network architecture can be implemented as a general mechanism for controlling transition rates and discuss applications in population studies of two differentiated cell lineages, ex: the myeloid/erythroid lineage in hematopoiesis.

The high-energy X-ray spectrum of black hole candidate GX 339-4 during a transition

NASA Technical Reports Server (NTRS)

Dolan, J. F.; Crannell, C. J.; Dennis, B. R.; Orwig, L. E.

1987-01-01

The X-ray emitting system GX 339-4 contains one of the prime candidates for a stellar mass-sized black hole. Determining the observational similarities and differences between the members of this group is of value in specifying which characteristics can be used to identify systems containing a black hole, especially those for which no mass determination can be made. The first observations of the E greater than 20 keV spectrum of GX 339-4 during a transition between luminosity states are reported here. The hard spectral state is the lower luminosity state of the system. GX 339-4 has a power-low spectrum above 20 keV which pivots during transitions between distinct luminosity states. The only other X-ray sources known to exhibit this behavior, Cyg XR-1 and (probably) A0620-00, are leading candidates for systems containing a black hole component based on their measured spectrocopic mass function.

Laser photoelectron spectroscopy of MnH - and FeH - : Electronic structures of the metal hydrides, identification of a low-spin excited state of MnH, and evidence for a low-spin ground state of FeH

NASA Astrophysics Data System (ADS)

Stevens, Amy E.; Feigerle, C. S.; Lineberger, W. C.

1983-05-01

The laser photoelectron spectra of MnH- and MnD-, and FeH- and FeD- are reported. A qualitative description of the electronic structure of the low-spin and high-spin states of the metal hydrides is developed, and used to interpret the spectra. A diagonal transition in the photodetachment to the known high-spin, 7Σ+, ground state of MnH is observed. An intense off-diagonal transition to a state of MnH, at 1725±50 cm-1 excitation energy, is attributed to loss of an antibonding electron from MnH-, to yield a low-spin quintet state of MnH. For FeH- the photodetachment to the ground state is an off-diagonal transition, attributed to loss of the antibonding electron from FeH-, to yield a low-spin quartet ground state of FeH. A diagonal transition results in an FeH state at 1945±55 cm-1; this state of FeH is assigned as the lowest-lying high-spin sextet state of FeH. An additional excited state of MnH and two other excited states of FeH are observed. Excitation energies for all the states are reported; vibrational frequencies and bond lengths for the ions and several states of the neutrals are also determined from the spectra. The electron affinity of MnH is found to be 0.869±0.010 eV; and the electron affinity of FeH is determined to be 0.934±0.011 eV. Spectroscopic constants for the various deuterides are also reported.

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni.

PubMed

Higgs, T D C; Bonetti, S; Ohldag, H; Banerjee, N; Wang, X L; Rosenberg, A J; Cai, Z; Zhao, J H; Moler, K A; Robinson, J W A

2016-07-22

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

DOE PAGES

Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; ...

2016-07-22

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using themore » element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. In conclusion, the results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.« less

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

NASA Astrophysics Data System (ADS)

Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; Banerjee, N.; Wang, X. L.; Rosenberg, A. J.; Cai, Z.; Zhao, J. H.; Moler, K. A.; Robinson, J. W. A.

2016-07-01

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

3 CFR - Presidential Determination on Major Illicit Drug Transit or Major Illicit Drug Producing...

Code of Federal Regulations, 2012 CFR

2012-01-01

... Venezuela are vital to the national interests of the United States. Afghanistan remains the world's largest... major transit country for opiates and hashish for markets around the world and is a transit country for... proximity to southern Europe provides a natural gateway to European drug markets. Porous borders, inadequate...

Rotational frequencies of transition metal hydrides for astrophysical searches in the far-infrared

NASA Technical Reports Server (NTRS)

Brown, John M.; Beaton, Stuart P.; Evenson, Kenneth M.

1993-01-01

Accurate frequencies for the lowest rotational transitions of five transition metal hydrides (CrH, FeH, CoH, NiH, and CuH) in their ground electronic states are reported to help the identification of these species in astrophysical sources from their far-infrared spectra. Accurate frequencies are determined in two ways: for CuH, by calculation from rotational constants determined from higher J transitions with an accuracy of 190 kHz; for the other species, by extrapolation to zero magnetic field from laser magnetic resonance spectra with an accuracy of 0.7 MHz.

The Structure of 34Mg Nuclei

NASA Astrophysics Data System (ADS)

Luna, Benjamin

2017-09-01

In the chart of nuclei below the beta-stability line, there are regions called islands of inversion where nuclei are expected have a spherical ground state, but it has been determined that these nuclei have a deformed ground state. This project was part of an ongoing investigation with the goal of obtaining new information about 34Mg and 34Al, which lie near an island of inversion. A beam of 34Mg was sent to the center of an array of plastic scintillators and HPGe detectors to collect data from the isotope's beta decay. This isotope beta decays to 34Al and to 34Si. The analysis softwares ROOT and GRSISort were used to sort the data into analysis trees, from which certain histograms were extracted. These histograms were used to determine an initial list of gamma ray transitions associated with the relatively fast decays of 34Mg and 34Al. Since the efficiencies of gamma ray detection are known, the true number of counts from each transition can be determined. This was done to order the gamma ray transitions into a nuclear level scheme. Future work on this subject will include the analysis of the angular correlations of the transitions found to determine spins of states populated in the 34Al and Si daughter nuclei as well as shedding light on the isomer in 34Al.

Frequency measurement of the 2 S10-3 D12 two-photon transition in atomic 4He

NASA Astrophysics Data System (ADS)

Huang, Yi-Jan; Guan, Yu-Chan; Huang, Yao-Chin; Suen, Te-Hwei; Peng, Jin-Long; Wang, Li-Bang; Shy, Jow-Tsong

2018-03-01

We present precise frequency measurement of the 2 S10-3 D12 two-photon transition in 4He at 1009 nm. The laser source at 1009 nm is stabilized on an optical frequency comb to perform the absolute frequency measurement. The absolute frequency of 2 S10-3 D12 transition is experimentally determined to be 594 414 291.803(13) MHz with a relative uncertainty of 1.6 ×10-11 , which is more precise than previous determinations by a factor of 25. In combination with the theoretical ionization energy of the 3 D12 state, the ionization energy of the 2 S10 state is determined to be 960 332 040.823(24) MHz. In addition, the deduced 2 S10 and 2 S31 Lamb shifts are 2806.864(24) MHz and 4058.130(24) MHz, respectively, which are 1.6 times better than previous determinations, and the fine structure 3 D31-3 D12 is determined to be 101 143.889(29) MHz, improving the precedent determination by a factor of 11.

Conductive interference in rapid transit signaling systems. volume 2. suggested test procedures

DOT National Transportation Integrated Search

1987-05-31

Methods for detecting and quantifying the levels of conductive electromagnetic interference produced by solid state rapid transit propulsion equipment and for determining the susceptibility of signaling systems to these emissions are presented. These...

Navigating ligand protein binding free energy landscapes: universality and diversity of protein folding and molecular recognition mechanisms

NASA Astrophysics Data System (ADS)

Verkhivker, Gennady M.; Rejto, Paul A.; Bouzida, Djamal; Arthurs, Sandra; Colson, Anthony B.; Freer, Stephan T.; Gehlhaar, Daniel K.; Larson, Veda; Luty, Brock A.; Marrone, Tami; Rose, Peter W.

2001-03-01

Thermodynamic and kinetic aspects of ligand-protein binding are studied for the methotrexate-dihydrofolate reductase system from the binding free energy profile constructed as a function of the order parameter. Thermodynamic stability of the native complex and a cooperative transition to the unique native structure suggest the nucleation kinetic mechanism at the equilibrium transition temperature. Structural properties of the transition state ensemble and the ensemble of nucleation conformations are determined by kinetic simulations of the transmission coefficient and ligand-protein association pathways. Structural analysis of the transition states and the nucleation conformations reconciles different views on the nucleation mechanism in protein folding.

Contribution of the 2(1)Ag state to the third-order optical nonlinearity in a squaraine dye.

PubMed

Andrews, J H; Khaydarov, J D; Singer, K D

1994-07-01

We have measured the third-harmonic response, gamma, of a centrosymmetric squaraine dye (ISQ) in chloroform at a range of frequencies for which the third harmonic is above the strong, narrow peak in the dye's linear absorption spectrum but below the UV absorption band. By fitting the experimental dispersion of gamma using a four-level model, we determine the strength, location, and width of the lowest-lying two-photon transition. We find that the 2(1)Ag state appears just above the 1(1)Bu state in energy and that the 1(1)Bu-2(1)Ag transition moment is somewhat smaller than the transition moment between the ground state and the 1(1)Bu state but much larger than previously predicted for comparable squaraine dyes.

Far-infrared laser magnetic resonance of vibrationally excited CD2

NASA Technical Reports Server (NTRS)

Evenson, K. M.; Sears, T. J.; Mckellar, A. R. W.

1984-01-01

The detection of 13 rotational transitions in the first excited bending state (010) of CD2 using the technique of far-infrared laser magnetic resonance spectroscopy is reported. Molecular parameters for this state are determined from these new data together with existing infrared observations of the v(2) band. Additional information on the ground vibrational state (000) is also provided by the observation of a new rotational transition, and this is combined with existing data to provide a refined set of molecular parameters for the CD2 ground state. One spectrum has been observed that is assigned as a rotational transition within the first excited symmetric stretching state (100) of CD2. These data will be of use in refining the structure and the potential function of the methylene radical.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Liang; Abild-Pedersen, Frank

On the basis of an extensive set of density functional theory calculations, it is shown that a simple scheme provides a fundamental understanding of variations in the transition state energies and structures of reaction intermediates on transition metal surfaces across the periodic table. The scheme is built on the bond order conservation principle and requires a limited set of input data, still achieving transition state energies as a function of simple descriptors with an error smaller than those of approaches based on linear fits to a set of calculated transition state energies. Here, we have applied this approach together withmore » linear scaling of adsorption energies to obtain the energetics of the NH 3 decomposition reaction on a series of stepped fcc(211) transition metal surfaces. Moreover, this information is used to establish a microkinetic model for the formation of N 2 and H 2, thus providing insight into the components of the reaction that determines the activity.« less

Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

PubMed

Robins, Lori I; Fogle, Emily J; Marlier, John F

2015-11-01

The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

Phase transition in conservative diffusive contact processes

NASA Astrophysics Data System (ADS)

Fiore, Carlos E.; de Oliveira, Mário J.

2004-10-01

We determine the phase diagrams of conservative diffusive contact processes by means of numerical simulations. These models are versions of the ordinary diffusive single-creation, pair-creation, and triplet-creation contact processes in which the particle number is conserved. The transition between the frozen and active states was determined by studying the system in the subcritical regime, and the nature of the transition, whether continuous or first order, was determined by looking at the fractal dimension of the critical cluster. For the single-creation model the transition remains continuous for any diffusion rate. For pair- and triplet-creation models, however, the transition becomes first order for high enough diffusion rate. Our results indicate that in the limit of infinite diffusion rate the jump in density equals 2/3 for the pair-creation model and 5/6 for the triplet-creation model.

Hydrogen-bonded intermediates and transition states during spontaneous and acid-catalyzed hydrolysis of the carcinogen (+)-anti-BPDE.

PubMed

Palenik, Mark C; Rodriguez, Jorge H

2014-07-07

Understanding mechanisms of (+)-anti-BPDE detoxification is crucial for combating its mutagenic and potent carcinogenic action. However, energetic-structural correlations of reaction intermediates and transition states during detoxification via hydrolysis are poorly understood. To gain mechanistic insight we have computationally characterized intermediate and transition species associated with spontaneous and general-acid catalyzed hydrolysis of (+)-anti-BPDE. We studied the role of cacodylic acid as a proton donor in the rate limiting step. The computed activation energy (ΔG‡) is in agreement with the experimental value for hydrolysis in a sodium cacodylate buffer. Both types of, spontaneous and acid catalyzed, BPDE hydrolysis can proceed through low-entropy hydrogen bonded intermediates prior to formation of transition states whose energies determine reaction activation barriers and rates.

Crystal structure of the unactivated ribulose 1,5-bisphosphate carboxylase/oxygenase complexed with a transition state analog, 2-carboxy-D-arabinitol 1,5-bisphosphate.

PubMed Central

Zhang, K. Y.; Cascio, D.; Eisenberg, D.

1994-01-01

The crystal structure of unactivated ribulose 1,5-bisphosphate carboxylase/oxygenase from Nicotiana tabacum complexed with a transition state analog, 2-carboxy-D-arabinitol 1,5-bisphosphate, was determined to 2.7 A resolution by X-ray crystallography. The transition state analog binds at the active site in an extended conformation. As compared to the binding of the same analog in the activated enzyme, the analog binds in a reverse orientation. The active site Lys 201 is within hydrogen bonding distance of the carboxyl oxygen of the analog. Loop 6 (residues 330-339) remains open and flexible upon binding of the analog in the unactivated enzyme, in contrast to the closed and ordered loop 6 in the activated enzyme complex. The transition state analog is exposed to solvent due to the open conformation of loop 6. PMID:8142899

Minimum Action Path Theory Reveals the Details of Stochastic Transitions Out of Oscillatory States

NASA Astrophysics Data System (ADS)

de la Cruz, Roberto; Perez-Carrasco, Ruben; Guerrero, Pilar; Alarcon, Tomas; Page, Karen M.

2018-03-01

Cell state determination is the outcome of intrinsically stochastic biochemical reactions. Transitions between such states are studied as noise-driven escape problems in the chemical species space. Escape can occur via multiple possible multidimensional paths, with probabilities depending nonlocally on the noise. Here we characterize the escape from an oscillatory biochemical state by minimizing the Freidlin-Wentzell action, deriving from it the stochastic spiral exit path from the limit cycle. We also use the minimized action to infer the escape time probability density function.

Minimum Action Path Theory Reveals the Details of Stochastic Transitions Out of Oscillatory States.

PubMed

de la Cruz, Roberto; Perez-Carrasco, Ruben; Guerrero, Pilar; Alarcon, Tomas; Page, Karen M

2018-03-23

Cell state determination is the outcome of intrinsically stochastic biochemical reactions. Transitions between such states are studied as noise-driven escape problems in the chemical species space. Escape can occur via multiple possible multidimensional paths, with probabilities depending nonlocally on the noise. Here we characterize the escape from an oscillatory biochemical state by minimizing the Freidlin-Wentzell action, deriving from it the stochastic spiral exit path from the limit cycle. We also use the minimized action to infer the escape time probability density function.

Spectroscopic parameters, vibrational levels, transition dipole moments and transition probabilities of the 9 low-lying states of the NCl+ cation

NASA Astrophysics Data System (ADS)

Yin, Yuan; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue

2018-03-01

This work calculates the potential energy curves of 9 Λ-S and 28 Ω states of the NCl+ cation. The technique employed is the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction. The Λ-S states are X2Π, 12Σ+, 14Π, 14Σ+, 14Σ-, 24Π, 14Δ, 16Σ+, and 16Π, which are yielded from the first two dissociation channels of NCl+ cation. The Ω states are generated from these Λ-S states. The 14Π, 14Δ, 16Σ+, and 16Π states are inverted with the spin-orbit coupling effect included. The 14Σ+, 16Σ+, and 16Π states are very weakly bound, whose well depths are only several-hundred cm- 1. One avoided crossing of PECs occurs between the 12Σ+ and 22Σ+ states. To improve the quality of potential energy curves, core-valence correlation and scalar relativistic corrections are included. The potential energies are extrapolated to the complete basis set limit. The spectroscopic parameters and vibrational levels are calculated. The transition dipole moments are computed. The Franck-Condon factors, Einstein coefficients, and radiative lifetimes of many transitions are determined. The spectroscopic approaches are proposed for observing these states according to the transition probabilities. The spin-orbit coupling effect on the spectroscopic and vibrational properties is evaluated. The spectroscopic parameters, vibrational levels, transition dipole moments, as well as transition probabilities reported in this paper could be considered to be very reliable.

New Transition in the Vortex Liquid State: intrinsic limit of the irreversibility line

NASA Astrophysics Data System (ADS)

Kwok, Wai-Kwong; Paulius, Lisa; Figueras, Jordi

2005-03-01

We have carried out angular dependent magneto-transport measurements on optimally doped, untwinned YBCO crystals irradiated with high energy heavy ions to determine the onset of vortex line tension in the vortex liquid state. The matching field was controlled and kept at a low level to partially preserve the first order vortex lattice melting transition. A Bose glass transition is observed below the lower critical point which then transforms into a first order phase transition near 5 Tesla. The locus of points which indicate the onset of vortex line tension overlaps with the Bose glass transition line at low fields and then deviates at higher fields, indicating a new transition line in the vortex liquid state. This new line in the vortex liquid phase extends beyond the upper critical point.This work was supported by the U.S. Department of Energy, BES, Materials Science under Contract No. W-31-109-ENG-38 at Argonne National Laboratory.

An Examination of the Mixing of Low-Lying Excited 0+ States in 116Sn

NASA Astrophysics Data System (ADS)

Pore, Jennifer Louise

The even-even tin isotopes are known to exhibit shape coexistence, the phenomenon where multiple shapes coexist in a narrow energy region at relatively lowlying levels of the nucleus. These nuclei have a 0+ spherical ground state and multiple excited 0+ states, one of which is a band head for a deformed rotational band, caused by the promotion of two protons across the Z=50 shell gap. Experimental and theoretical investigations have been performed on 116Sn to describe the nature of the mixing that occurs between the vibrational phonon levels and the deformed rotational band by probing the character of the excited 0+ states. At the time it was thought that the 0+ states showed almost equal mixing of rotational and vibrational character, but this result was based on an indirect observation and fit of the intensity of a weak 85 keV transition. The current work, a high-statistics 116Sn measurement, demonstrates unequal mixing of character between the two excited 0+ states based on a direct measurement of the intensity of the 85 keV transition. These new results might prompt a new interpretation of the structure of 116Sn. The experiment to investigate the low-lying structure of 116Sn was conducted at TRIUMF, Canada's National Laboratory for Nuclear and Particle Physics. A highintensity and high-purity beam of 116In was used to populate states in 116Sn via beta decay. The resulting gamma rays were observed with the 8th detector array, which consists of twenty high-purity Compton-suppressed germanium detectors coupled to a suite of ancillary detectors for beta particle detection and conversion electron spectroscopy. From this high-statistics measurement 57 gamma-ray transitions were observed, with 4 new transitions that depopulate the 3096 keV level observed for the first time with energies of 101 keV, 296 keV, 447 keV, and 871 keV. Branching ratios were determined for all of the observed transitions. For the 57 transitions observed, a relative intensity had not been reported for 17 of them, and a branching ratio had not been reported for 12 of them. Transition rates were determined for 25 transitions that depopulate levels with previously reported lifetimes, and 2 of these transition rates had not been previously observed.

45 CFR 150.221 - Transition to State enforcement.

Code of Federal Regulations, 2010 CFR

2010-10-01

... ACCESS CMS ENFORCEMENT IN GROUP AND INDIVIDUAL INSURANCE MARKETS CMS Enforcement Processes for... State enforcement. (a) If CMS determines that a State for which it has assumed enforcement authority has... appropriate to return enforcement authority to the State, CMS will enter into discussions with State officials...

PCR evaluation : considering transition from manual to semi-automated pavement distress collection and analysis.

DOT National Transportation Integrated Search

2013-07-01

This study is designed to assist the Ohio Department of Transportation (ODOT) in determining : whether transitioning from manual to state-of the-practice semi-automated pavement distress : data collection is feasible and recommended. Statistical and ...

MARVEL analysis of the measured high-resolution rovibrational spectra of C2H2

NASA Astrophysics Data System (ADS)

Chubb, Katy L.; Joseph, Megan; Franklin, Jack; Choudhury, Naail; Furtenbacher, Tibor; Császár, Attila G.; Gaspard, Glenda; Oguoko, Patari; Kelly, Adam; Yurchenko, Sergei N.; Tennyson, Jonathan; Sousa-Silva, Clara

2018-01-01

Rotation-vibration energy levels are determined for the electronic ground state of the acetylene molecule, 12C2H2, using the Measured Active Rotational-Vibrational Energy Levels (MARVEL) technique. 37,813 measured transitions from 61 publications are considered. The distinct components of the spectroscopic network linking ortho and para states of the molecule are considered separately. The 20,717 ortho and 17,096 para transitions measured experimentally are used to determine 6013 ortho and 5200 para energy levels. The MARVEL results are compared with alternative compilations based on the use of effective Hamiltonians.

Pseudo-direct bandgap transitions in silicon nanocrystals: effects on optoelectronics and thermoelectrics

NASA Astrophysics Data System (ADS)

Singh, Vivek; Yu, Yixuan; Sun, Qi-C.; Korgel, Brian; Nagpal, Prashant

2014-11-01

While silicon nanostructures are extensively used in electronics, the indirect bandgap of silicon poses challenges for optoelectronic applications like photovoltaics and light emitting diodes (LEDs). Here, we show that size-dependent pseudo-direct bandgap transitions in silicon nanocrystals dominate the interactions between (photoexcited) charge carriers and phonons, and hence the optoelectronic properties of silicon nanocrystals. Direct measurements of the electronic density of states (DOS) for different sized silicon nanocrystals reveal that these pseudo-direct transitions, likely arising from the nanocrystal surface, can couple with the quantum-confined silicon states. Moreover, we demonstrate that since these transitions determine the interactions of charge carriers with phonons, they change the light emission, absorption, charge carrier diffusion and phonon drag (Seebeck coefficient) in nanoscaled silicon semiconductors. Therefore, these results can have important implications for the design of optoelectronics and thermoelectric devices based on nanostructured silicon.While silicon nanostructures are extensively used in electronics, the indirect bandgap of silicon poses challenges for optoelectronic applications like photovoltaics and light emitting diodes (LEDs). Here, we show that size-dependent pseudo-direct bandgap transitions in silicon nanocrystals dominate the interactions between (photoexcited) charge carriers and phonons, and hence the optoelectronic properties of silicon nanocrystals. Direct measurements of the electronic density of states (DOS) for different sized silicon nanocrystals reveal that these pseudo-direct transitions, likely arising from the nanocrystal surface, can couple with the quantum-confined silicon states. Moreover, we demonstrate that since these transitions determine the interactions of charge carriers with phonons, they change the light emission, absorption, charge carrier diffusion and phonon drag (Seebeck coefficient) in nanoscaled silicon semiconductors. Therefore, these results can have important implications for the design of optoelectronics and thermoelectric devices based on nanostructured silicon. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04688a

Study on the spectroscopic parameters and transition probabilities of 25 low-lying states of the AlC+ cation

NASA Astrophysics Data System (ADS)

Zhang, Jicai; Shi, Deheng; Xing, Wei; Sun, Jinfeng; Zhu, Zunlue

2017-11-01

This paper investigates the spectroscopic parameters and transition probabilities of 25 low-lying states, which come from the first five dissociation channels of AlC+ cation. The potential energy curves are calculated with the complete active space self-consistent field method, which is followed by the valence internally contracted multireference configuration interaction approach with Davidson correction. Of these 25 states, only the 35Σ-state is repulsive; the c1Σ+, f1Π, and 15Π states have the double well; the first well of c1Σ+ state and the second well of 15Π state are very weakly bound; the first well of c1Σ+ state has no vibrational levels; the 25Π state and the double well of f1Π state have only several vibrational states; the B3Σ-, E3Σ+, D3Π, 15Σ+, 25Σ-, and 15Π states are inverted when the spin-orbit coupling effect is included. The avoided crossings exist between the B3Σ- and 33Σ- states, the c1Σ+ and d1Σ+ states, the f1Π and 31Π states, the 15Π and 25Π states, as well as the 25Π and 35Π states. Core-valence correlation and scalar relativistic corrections are considered. The extrapolation of potential energies to the complete basis set limit is done. The spectroscopic parameters and vibrational levels are determined for all the Λ-S and Ω bound states. The transition dipole moments are calculated. Franck-Condon factors of a great number of electronic transitions are evaluated. On the whole, the spin-orbit coupling effect on the spectroscopic parameters and vibrational levels is small except for very few states. The results determined in this paper could provide some powerful guidelines to observe these states in a spectroscopy experiment.

The Galactic Black Hole Transient H1743-322 During Outburst Decay Connections Between Timing Noise, State Transitions, And Radio Emission

NASA Technical Reports Server (NTRS)

Kalemci, E.; Tomsick, J. A.; Corbel; Kaaret, P.; Rothschild, R. E.; Pottschmidt, K.

2006-01-01

Multiwavelength observations of Galactic black hole transients during outburst decay are instrumental for our understanding of the accretion geometry and the formation of outflows around black hole systems. H1743-322, a black hole transient observed intensely in X-rays and also covered in the radio band during its 2003 decay, provides clues about the changes in accretion geometry during state transitions and also the general properties of X-ray emission during the intermediate and low-hard states. In this work, we report on the evolution of spectral and temporal properties in X-rays and the flux in the radio band, with the goal of understanding the nature of state transitions observed in this source. We concentrate on the transition from the thermal dominant state to the intermediate state that occurs on a timescale of 1 day. We show that the state transition is associated with a sudden increase in power-law flux. We determine that the ratio of the power-law flux to the overall flux in the 3-25 keV band must exceed 0.6 for us to observe strong timing noise. Even after the state transition, once this ratio was below 0.6, the system transited back to the thermal dominant state for 1 day. We show that the emission from the compact radio core does not turn on during the transition from the thermal dominant state to the intermediate state but does turn on when the source reaches the low-hard state, as seen in 4U 1543-47 and GX 339-4. We find that the photon index correlates strongly with the QPO frequency and anticorrelates with the rms amplitude of variability. We also show that the variability is more likely to be associated with the power-law emission than the disk emission.

A specific transition state for S-peptide combining with folded S-protein and then refolding

PubMed Central

Goldberg, Jonathan M.; Baldwin, Robert L.

1999-01-01

We measured the folding and unfolding kinetics of mutants for a simple protein folding reaction to characterize the structure of the transition state. Fluorescently labeled S-peptide analogues combine with S-protein to form ribonuclease S analogues: initially, S-peptide is disordered whereas S-protein is folded. The fluorescent probe provides a convenient spectroscopic probe for the reaction. The association rate constant, kon, and the dissociation rate constant, koff, were both determined for two sets of mutants. The dissociation rate constant is measured by adding an excess of unlabeled S-peptide analogue to a labeled complex (RNaseS*). This strategy allows kon and koff to be measured under identical conditions so that microscopic reversibility applies and the transition state is the same for unfolding and refolding. The first set of mutants tests the role of the α-helix in the transition state. Solvent-exposed residues Ala-6 and Gln-11 in the α-helix of native RNaseS were replaced by the helix destabilizing residues glycine or proline. A plot of log kon vs. log Kd for this series of mutants is linear over a very wide range, with a slope of −0.3, indicating that almost all of the molecules fold via a transition state involving the helix. A second set of mutants tests the role of side chains in the transition state. Three side chains were investigated: Phe-8, His-12, and Met-13, which are known to be important for binding S-peptide to S-protein and which also contribute strongly to the stability of RNaseS*. Only the side chain of Phe-8 contributes significantly, however, to the stability of the transition state. The results provide a remarkably clear description of a folding transition state. PMID:10051587

Hyperfine-resolved transition frequency list of fundamental vibration bands of H35Cl and H37Cl

NASA Astrophysics Data System (ADS)

Iwakuni, Kana; Sera, Hideyuki; Abe, Masashi; Sasada, Hiroyuki

2014-12-01

Sub-Doppler resolution spectroscopy of the fundamental vibration bands of H35Cl and H37Cl has been carried out from 87.1 to 89.9 THz. We have determined the absolute transition frequencies of the hyperfine-resolved R(0) to R(4) transitions with a typical uncertainty of 10 kHz. We have also yielded six molecular constants for each isotopomer in the vibrational excited state, which reproduce the determined frequencies with a standard deviation of about 10 kHz.

Phase transitions in neutron star equation of state induced by the delta resonances matter

NASA Astrophysics Data System (ADS)

T, Oliveira J. C.; Rodrigues, H.; Duarte, S. B.

2016-04-01

In the present work we determine the equation of state and the population of baryons and leptons, and also we discuss the implication of changes in the baryon-meson coupling constants to the formation of delta matter in the stellar medium. And also in this work the phase transition is explored with respect to the domain of the delta-mesons coupling constants.

State of the Art of Current Practices for Transit Transfers.

DOT National Transportation Integrated Search

1981-07-01

The major objectives of the study are to: (1) describe and summarize the transfer policies currently in use on U.S. transit properties; (2) identify reasons why properties use or do not use particular transfer policies; (3) determine the consequences...

Theoretical studies of the transition state structures and free energy barriers for base-catalyzed hydrolysis of amides

PubMed Central

Xiong, Ying; Zhan, Chang-Guo

2010-01-01

The transition state structures and free energy barriers for the rate-determining step (i.e. the formation of a tetrahedral intermediate) of base-catalyzed hydrolysis of a series of amides in aqueous solution have been studied by performing first-principle electronic structure calculations using a hybrid supermolecule-polarizable continuum approach. The calculated results and a revisit of recently reported experimental proton inventory data reveal that the favorable transition state structure optimized for the tetrahedral intermediate formation of hydroxide ion-catalyzed hydrolysis of formamide may have three solvating water molecules remaining on the attacking hydroxide oxygen and two additional water molecules attached to the carbonyl oxygen of formamide. The calculated results have also demonstrated interesting substituent effects on the optimized transition state geometries, on the transition-state stabilization, and on the calculated free energy barriers for the base-catalyzed hydrolysis of amides. When some or all of the hydrogen atoms of formamide are replaced by methyl groups, the total number of water molecules hydrogen-bonding with the attacking hydroxide in the transition state decreases from three for formamide to two for N-methylacetamide, N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA). The larger substituents of the amide hinder the solvent water molecules approaching the attacking hydroxide oxygen in the transition state and, therefore, destabilize the transition state structure and increase the free energy barrier. By using the optimized most favorable transition state structures, the calculated free energy barriers, i.e. 21.6 (or 21.7), 22.7, 23.1, and 26.0 kcal/mol for formamide, N-methylacetamide, DMF, and DMA, respectively, are in good agreement with the available experimental free energy barriers, i.e. 21.2, 21.5, 22.6, and 24.1 kcal/mol for formamide, N-methylacetamide, DMF, and DMA, respectively. PMID:17107116

Transition metal ions in ZnO: Effects of intrashell coulomb repulsion on electronic properties

NASA Astrophysics Data System (ADS)

Ciechan, A.; Bogusławski, P.

2018-05-01

Electronic structure of the transition metal (TM) dopants in ZnO is calculated by first principles approach. Analysis of the results is focused on the properties determined by the intrashell Coulomb coupling. The role of both direct and exchange interaction channel is analyzed. The coupling is manifested in the strong charge state dependence of the TM gap levels, which leads to the metastability of photoexcited Mn, and determines the accessible equilibrium charge states of TM ions. The varying magnitude of the exchange coupling is reflected in the dependence of the spin splitting energy on the chemical identity across the 3d series, as well as the charge state dependence of spin-up spin-down exchange splitting.

Coupled channels description of the α-decay fine structure

NASA Astrophysics Data System (ADS)

Delion, D. S.; Ren, Zhongzhou; Dumitrescu, A.; Ni, Dongdong

2018-05-01

We review the coupled channels approach of α transitions to excited states. The α-decaying states are identified as narrow outgoing Gamow resonances in an α-daughter potential. The real part of the eigenvalue corresponds to the Q-value, while the imaginary part determines the half of the total α-decay width. We first review the calculations describing transitions to rotational states treated by the rigid rotator model, in even–even, odd-mass and odd–odd nuclei. It is found that the semiclassical method overestimates the branching ratios to excited 4+ for some even–even α-emitters and fails in explaining the unexpected inversion of branching ratios of some odd-mass nuclei, while the coupled-channels results show good agreement with the experimental data. Then, we review the coupled channels method for α-transitions to 2+ vibrational and transitional states. We present the results of the Coherent State Model that describes in a unified way the spectra of vibrational, transitional and rotational nuclei. We evidence general features of the α-decay fine structure, namely the linear dependence between α-intensities and excitation energy, the linear correlation between the strength of the α-core interaction and spectroscopic factor, and the inverse correlation between the nuclear collectivity, given by electromagnetic transitions, and α-clustering.

A residue in helical conformation in the native state adopts a β-strand conformation in the folding transition state despite its high and canonical Φ-value.

PubMed

Zarrine-Afsar, Arash; Dahesh, Samira; Davidson, Alan R

2012-05-01

Delineating structures of the transition states in protein folding reactions has provided great insight into the mechanisms by which proteins fold. The most common method for obtaining this information is Φ-value analysis, which is carried out by measuring the changes in the folding and unfolding rates caused by single amino acid substitutions at various positions within a given protein. Canonical Φ-values range between 0 and 1, and residues displaying high values within this range are interpreted to be important in stabilizing the transition state structure, and to elicit this stabilization through native-like interactions. Although very successful in defining the general features of transition state structures, Φ-value analysis can be confounded when non-native interactions stabilize this state. In addition, direct information on backbone conformation within the transition state is not provided. In the work described here, we have investigated structure formation at a conserved β-bulge (with helical conformation) in the Fyn SH3 domain by characterizing the effects of substituting all natural amino acids at one position within this structural motif. By comparing the effects on folding rates of these substitutions with database-derived local structure propensity values, we have determined that this position adopts a non-native backbone conformation in the folding transition state. This result is surprising because this position displays a high and canonical Φ-value of 0.7. This work emphasizes the potential role of non-native conformations in folding pathways and demonstrates that even positions displaying high and canonical Φ-values may, nevertheless, adopt a non-native conformation in the transition state. Copyright © 2012 Wiley Periodicals, Inc.

Slow photoelectron imaging spectroscopy of CCO- and CCS-.

PubMed

Garand, Etienne; Yacovitch, Tara I; Neumark, Daniel M

2008-08-21

High-resolution photodetachment spectra of CCO(-) and CCS(-) using slow photoelectron velocity-map imaging spectroscopy are reported. Well-resolved transitions to the neutral X (3)Sigma(-), a (1)Delta, b (1)Sigma(+), and A (3)Pi states are seen for both species. The electron affinities of CCO and CCS are determined to be 2.3107+/-0.0006 and 2.7475+/-0.0006 eV, respectively, and precise term energies for the a (1)Delta, b (1)Sigma(+), and A (3)Pi excited states are also determined. The two low-lying singlet states of CCS are observed for the first time, as are several vibronic transitions within the four bands. Analysis of hot bands finds the spin-orbit orbit splitting in the X (2)Pi ground state of CCO(-) and CCS(-) to be 61 and 195 cm(-1), respectively.

Laser Induced Optical Pumping Measurements of Cross Sections for Fine and Hyperfine Structure Transitions in Sodium Induced by Collisions with Helium Argon Atoms

NASA Technical Reports Server (NTRS)

Dobson, Chris C.; Sung, C. C.

1998-01-01

Optical pumping of the ground states of sodium can radically alter the shape of the laser induced fluorescence excitation spectrum, complicating measurements of temperature, pressure, etc., which are based on these spectra. Modeling of the fluorescence using rate equations for the eight hyperfine states of the sodium D manifolds can be used to quantify the contribution to the ground state pumping of transitions among the hyperfine excited states induced by collisions with buffer gas atoms. This model is used here to determine, from the shape of experimental spectra, cross sections for (Delta)F transitions of the P(sub 3/2) state induced by collisions with helium and argon atoms, for a range of values assumed for the P(sub 1/2), (Delta)F cross sections. The hyperfine cross sections measured using this method, which is thought to be novel, are compared with cross sections for transitions involving polarized magnetic substates, m(sub F), measured previously using polarization sensitive absorption. Also, fine structure transition ((Delta)J) cross sections were measured in the pumped vapor, giving agreement with previous measurements made in the absence of pumping.

Laser-Induced Optical Pumping Measurements of Cross Section for Fine- and Hyperfine-Structure Transitions in Sodium Induced by Collisions with Helium and Argon Atoms

NASA Technical Reports Server (NTRS)

Dobson, Chris C.; Sung, C. C.

1999-01-01

Optical pumping of the ground states of sodium can radically alter the shape of the laser-induced fluorescence excitation spectrum, complicating measurements of temperature, pressure, etc., which are based on these spectra. Modeling of the fluorescence using rate equations for the eight hyperfine states of the sodium D manifolds can be used to quantify the contribution to the ground state pumping of transitions among the hyperfine excited states induced by collisions with buffer gas atoms. This model is used here to determine, from the shape of experimental spectra, cross sections lor DELTA.F transitions of the P(sub 3/2) state induced by collisions with helium and argon atoms, for a range of values assumed for the P(sub 1/2), DELTA.F cross sections. The hyperfine cross sections measured using this method, which to our knowledge is novel, are compared with cross sections for transitions involving polarized magnetic substates m(sub F) measured previously using polarization sensitive absorption. Also, fine-structure transition cross sections were measured in the pumped vapor, giving agreement with previous measurements made in the absence of pumping.

Synaptic plasticity modulates autonomous transitions between waking and sleep states: Insights from a Morris-Lecar model

NASA Astrophysics Data System (ADS)

Ciszak, Marzena; Bellesi, Michele

2011-12-01

The transitions between waking and sleep states are characterized by considerable changes in neuronal firing. During waking, neurons fire tonically at irregular intervals and a desynchronized activity is observed at the electroencephalogram. This activity becomes synchronized with slow wave sleep onset when neurons start to oscillate between periods of firing (up-states) and periods of silence (down-states). Recently, it has been proposed that the connections between neurons undergo potentiation during waking, whereas they weaken during slow wave sleep. Here, we propose a dynamical model to describe basic features of the autonomous transitions between such states. We consider a network of coupled neurons in which the strength of the interactions is modulated by synaptic long term potentiation and depression, according to the spike time-dependent plasticity rule (STDP). The model shows that the enhancement of synaptic strength between neurons occurring in waking increases the propensity of the network to synchronize and, conversely, desynchronization appears when the strength of the connections become weaker. Both transitions appear spontaneously, but the transition from sleep to waking required a slight modification of the STDP rule with the introduction of a mechanism which becomes active during sleep and changes the proportion between potentiation and depression in accordance with biological data. At the neuron level, transitions from desynchronization to synchronization and vice versa can be described as a bifurcation between two different states, whose dynamical regime is modulated by synaptic strengths, thus suggesting that transition from a state to an another can be determined by quantitative differences between potentiation and depression.

Mechanism and the origins of stereospecificity in copper-catalyzed ring expansion of vinyl oxiranes: a traceless dual transition-metal-mediated process.

PubMed

Mustard, Thomas J L; Mack, Daniel J; Njardarson, Jon T; Cheong, Paul Ha-Yeon

2013-01-30

Density functional theory computations of the Cu-catalyzed ring expansion of vinyloxiranes is mediated by a traceless dual Cu(I)-catalyst mechanism. Overall, the reaction involves a monomeric Cu(I)-catalyst, but a single key step, the Cu migration, requires two Cu(I)-catalysts for the transformation. This dual-Cu step is found to be a true double Cu(I) transition state rather than a single Cu(I) transition state in the presence of an adventitious, spectator Cu(I). Both Cu(I) catalysts are involved in the bond forming and breaking process. The single Cu(I) transition state is not a stationary point on the potential energy surface. Interestingly, the reductive elimination is rate-determining for the major diastereomeric product, while the Cu(I) migration step is rate-determining for the minor. Thus, while the reaction requires dual Cu(I) activation to proceed, kinetically, the presence of the dual-Cu(I) step is untraceable. The diastereospecificity of this reaction is controlled by the Cu migration step. Suprafacial migration is favored over antarafacial migration due to the distorted Cu π-allyl in the latter.

First Determination of the Level Structure of an s d -Shell Hypernucleus, F19Λ

NASA Astrophysics Data System (ADS)

Yang, S. B.; Ahn, J. K.; Akazawa, Y.; Aoki, K.; Chiga, N.; Ekawa, H.; Evtoukhovitch, P.; Feliciello, A.; Fujita, M.; Hasegawa, S.; Hayakawa, S.; Hayakawa, T.; Honda, R.; Hosomi, K.; Hwang, S. H.; Ichige, N.; Ichikawa, Y.; Ikeda, M.; Imai, K.; Ishimoto, S.; Kanatsuki, S.; Kim, S. H.; Kinbara, S.; Kobayashi, K.; Koike, T.; Lee, J. Y.; Miwa, K.; Moon, T. J.; Nagae, T.; Nakada, Y.; Nakagawa, M.; Ogura, Y.; Sakaguchi, A.; Sako, H.; Sasaki, Y.; Sato, S.; Shirotori, K.; Sugimura, H.; Suto, S.; Suzuki, S.; Takahashi, T.; Tamura, H.; Tanida, K.; Togawa, Y.; Tsamalaidze, Z.; Ukai, M.; Wang, T. F.; Yamamoto, T. O.; J-PARC E13 Collaboration

2018-03-01

We report on the first observation of γ rays emitted from an s d -shell hypernucleus, F19Λ . The energy spacing between the ground state doublet, 1 /2+ and 3 /2+ states, of F19Λ is determined to be 315.5 ±0.4 (stat )-0.5+0.6(syst ) keV by measuring the γ -ray energy of the M 1 (3 /2+→1 /2+) transition. In addition, three γ -ray peaks are observed and assigned as E 2 (5 /2+→1 /2+), E 1 (1 /2-→1 /2+), and E 1 (1 /2-→3 /2+) transitions. The excitation energies of the 5 /2+ and 1 /2- states are determined to be 895.2 ±0.3 (stat )±0.5 (syst ) and 1265.6 ±1.2 (stat )-0.5+0.7(syst ) keV , respectively. It is found that the ground state doublet spacing is well described by theoretical models based on existing s - and p -shell hypernuclear data.

Engineered Bi-Histidine Metal Chelation Sites Map the Structure of the Mechanical Unfolding Transition State of an Elastomeric Protein Domain GB1

PubMed Central

Shen, Tao; Cao, Yi; Zhuang, Shulin; Li, Hongbin

2012-01-01

Determining the structure of the transition state is critical for elucidating the mechanism behind how proteins fold and unfold. Due to its high free energy, however, the transition state generally cannot be trapped and studied directly using traditional structural biology methods. Thus, characterizing the structure of the transition state that occurs as proteins fold and unfold remains a major challenge. Here, we report a novel (to our knowledge) method that uses engineered bi-histidine (bi-His) metal-binding sites to directly map the structure of the mechanical unfolding transition state of proteins. This method is adapted from the traditional ψ-value analysis, which uses engineered bi-His metal chelation sites to probe chemical (un)folding transition-state structure. The ϕM2+U-value is defined as ΔΔG‡-N/ΔΔGU-N, which is the energetic effects of metal chelation by the bi-His site on the unfolding energy barrier (ΔG‡-N) relative to its thermodynamic stability (ΔGU-N) and can be used to obtain information about the transition state in the mutational site. As a proof of principle, we used the small protein GB1 as a model system and set out to map its mechanical unfolding transition-state structure. Using single-molecule atomic force microscopy and spectrofluorimetry, we directly quantified the effect of divalent metal ion binding on the mechanical unfolding free energy and thermodynamic stability of GB1, which allowed us to quantify ϕM2+U-values for different sites in GB1. Our results enabled us to map the structure of the mechanical unfolding transition state of GB1. Within GB1’s mechanical unfolding transition state, the interface between force-bearing β-strands 1 and 4 is largely disrupted, and the first β-hairpin is partially disordered while the second β-hairpin and the α-helix remain structured. Our results demonstrate the unique application of ψ-value analysis in elucidating the structure of the transition state that occurs during the mechanical unfolding process, offering a potentially powerful new method for investigating the design of novel elastomeric proteins. PMID:22947942

Engineered bi-histidine metal chelation sites map the structure of the mechanical unfolding transition state of an elastomeric protein domain GB1.

PubMed

Shen, Tao; Cao, Yi; Zhuang, Shulin; Li, Hongbin

2012-08-22

Determining the structure of the transition state is critical for elucidating the mechanism behind how proteins fold and unfold. Due to its high free energy, however, the transition state generally cannot be trapped and studied directly using traditional structural biology methods. Thus, characterizing the structure of the transition state that occurs as proteins fold and unfold remains a major challenge. Here, we report a novel (to our knowledge) method that uses engineered bi-histidine (bi-His) metal-binding sites to directly map the structure of the mechanical unfolding transition state of proteins. This method is adapted from the traditional ψ-value analysis, which uses engineered bi-His metal chelation sites to probe chemical (un)folding transition-state structure. The φ(M2+)(U)-value is defined as ΔΔG(‡-N)/ΔΔG(U-N), which is the energetic effects of metal chelation by the bi-His site on the unfolding energy barrier (ΔG(‡-N)) relative to its thermodynamic stability (ΔG(U-N)) and can be used to obtain information about the transition state in the mutational site. As a proof of principle, we used the small protein GB1 as a model system and set out to map its mechanical unfolding transition-state structure. Using single-molecule atomic force microscopy and spectrofluorimetry, we directly quantified the effect of divalent metal ion binding on the mechanical unfolding free energy and thermodynamic stability of GB1, which allowed us to quantify φ(M2+)(U)-values for different sites in GB1. Our results enabled us to map the structure of the mechanical unfolding transition state of GB1. Within GB1's mechanical unfolding transition state, the interface between force-bearing β-strands 1 and 4 is largely disrupted, and the first β-hairpin is partially disordered while the second β-hairpin and the α-helix remain structured. Our results demonstrate the unique application of ψ-value analysis in elucidating the structure of the transition state that occurs during the mechanical unfolding process, offering a potentially powerful new method for investigating the design of novel elastomeric proteins. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Evaluation of sliding window correlation performance for characterizing dynamic functional connectivity and brain states

PubMed Central

Shakil, Sadia; Lee, Chin-Hui; Keilholz, Shella Dawn

2016-01-01

A promising recent development in the study of brain function is the dynamic analysis of resting-state functional MRI scans, which can enhance understanding of normal cognition and alterations that result from brain disorders. One widely used method of capturing the dynamics of functional connectivity is sliding window correlation (SWC). However, in the absence of a “gold standard” for comparison, evaluating the performance of the SWC in typical resting-state data is challenging. This study uses simulated networks (SNs) with known transitions to examine the effects of parameters such as window length, window offset, window type, noise, filtering, and sampling rate on the SWC performance. The SWC time course was calculated for all node pairs of each SN and then clustered using the k-means algorithm to determine how resulting brain states match known configurations and transitions in the SNs. The outcomes show that the detection of state transitions and durations in the SWC is most strongly influenced by the window length and offset, followed by noise and filtering parameters. The effect of the image sampling rate was relatively insignificant. Tapered windows provide less sensitivity to state transitions than rectangular windows, which could be the result of the sharp transitions in the SNs. Overall, the SWC gave poor estimates of correlation for each brain state. Clustering based on the SWC time course did not reliably reflect the underlying state transitions unless the window length was comparable to the state duration, highlighting the need for new adaptive window analysis techniques. PMID:26952197

A model of the normal and null states of pulsars

NASA Astrophysics Data System (ADS)

Jones, P. B.

1981-12-01

A solvable three-dimensional polar cap model of pair creation and charged particle acceleration has been derived. There are no free parameters of significance apart from the polar surface magnetic flux density. The parameter determining the acceleration potential difference has been obtained by calculation of elementary nuclear and electromagnetic processes. Solutions of the model exist for both normal and null states of a pulsar, and the instability in the normal state leading to the normal to null transition has been identified. The predicted necessary condition for the transition is entirely consistent with observation.

A model of the normal and null states of pulsars

NASA Astrophysics Data System (ADS)

Jones, P. B.

A solvable three dimensional polar cap model of pair creation and charged particle acceleration is derived. There are no free parameters of significance apart from the polar surface magnetic flux density. The parameter CO determining the acceleration potential difference was obtained by calculation of elementary nuclear and electromagnetic processes. Solutions of the model exist for both normal and null states of a pulsar, and the instability in the normal state leading to the normal to null transition is identified. The predicted necessary condition for the transition is entirely consistent with observation.

Hysteresis, reentrance, and glassy dynamics in systems of self-propelled rods

NASA Astrophysics Data System (ADS)

Kuan, Hui-Shun; Blackwell, Robert; Hough, Loren E.; Glaser, Matthew A.; Betterton, M. D.

2015-12-01

Nonequilibrium active matter made up of self-driven particles with short-range repulsive interactions is a useful minimal system to study active matter as the system exhibits collective motion and nonequilibrium order-disorder transitions. We studied high-aspect-ratio self-propelled rods over a wide range of packing fractions and driving to determine the nonequilibrium state diagram and dynamic properties. Flocking and nematic-laning states occupy much of the parameter space. In the flocking state, the average internal pressure is high and structural and mechanical relaxation times are long, suggesting that rods in flocks are in a translating glassy state despite overall flock motion. In contrast, the nematic-laning state shows fluidlike behavior. The flocking state occupies regions of the state diagram at both low and high packing fraction separated by nematic-laning at low driving and a history-dependent region at higher driving; the nematic-laning state transitions to the flocking state for both compression and expansion. We propose that the laning-flocking transitions are a type of glass transition that, in contrast to other glass-forming systems, can show fluidization as density increases. The fluid internal dynamics and ballistic transport of the nematic-laning state may promote collective dynamics of rod-shaped micro-organisms.

Hysteresis, reentrance, and glassy dynamics in systems of self-propelled rods.

PubMed

Kuan, Hui-Shun; Blackwell, Robert; Hough, Loren E; Glaser, Matthew A; Betterton, M D

2015-01-01

Nonequilibrium active matter made up of self-driven particles with short-range repulsive interactions is a useful minimal system to study active matter as the system exhibits collective motion and nonequilibrium order-disorder transitions. We studied high-aspect-ratio self-propelled rods over a wide range of packing fractions and driving to determine the nonequilibrium state diagram and dynamic properties. Flocking and nematic-laning states occupy much of the parameter space. In the flocking state, the average internal pressure is high and structural and mechanical relaxation times are long, suggesting that rods in flocks are in a translating glassy state despite overall flock motion. In contrast, the nematic-laning state shows fluidlike behavior. The flocking state occupies regions of the state diagram at both low and high packing fraction separated by nematic-laning at low driving and a history-dependent region at higher driving; the nematic-laning state transitions to the flocking state for both compression and expansion. We propose that the laning-flocking transitions are a type of glass transition that, in contrast to other glass-forming systems, can show fluidization as density increases. The fluid internal dynamics and ballistic transport of the nematic-laning state may promote collective dynamics of rod-shaped micro-organisms.

Bond Order Conservation Strategies in Catalysis Applied to the NH 3 Decomposition Reaction

DOE PAGES

Yu, Liang; Abild-Pedersen, Frank

2016-12-14

On the basis of an extensive set of density functional theory calculations, it is shown that a simple scheme provides a fundamental understanding of variations in the transition state energies and structures of reaction intermediates on transition metal surfaces across the periodic table. The scheme is built on the bond order conservation principle and requires a limited set of input data, still achieving transition state energies as a function of simple descriptors with an error smaller than those of approaches based on linear fits to a set of calculated transition state energies. Here, we have applied this approach together withmore » linear scaling of adsorption energies to obtain the energetics of the NH 3 decomposition reaction on a series of stepped fcc(211) transition metal surfaces. Moreover, this information is used to establish a microkinetic model for the formation of N 2 and H 2, thus providing insight into the components of the reaction that determines the activity.« less

Two-Dimensional Wetting Transition Modeling with the Potts Model

NASA Astrophysics Data System (ADS)

Lopes, Daisiane M.; Mombach, José C. M.

2017-12-01

A droplet of a liquid deposited on a surface structured in pillars may have two states of wetting: (1) Cassie-Baxter (CB), the liquid remains on top of the pillars, also known as heterogeneous wetting, or (2) Wenzel, the liquid fills completely the cavities of the surface, also known as homogeneous wetting. Studies show that between these two states, there is an energy barrier that, when overcome, results in the transition of states. The transition can be achieved by changes in geometry parameters of the surface, by vibrations of the surface or by evaporation of the liquid. In this paper, we present a comparison of two-dimensional simulations of the Cassie-Wenzel transition on pillar-structured surfaces using the cellular Potts model (CPM) with studies performed by Shahraz et al. In our work, we determine a transition diagram by varying the surface parameters such as the interpillar distance ( G) and the pillar height ( H). Our results were compared to those obtained by Shahraz et al. obtaining good agreement.

The mechanism of the converter domain rotation in the recovery stroke of myosin motor protein

PubMed Central

Baumketner, Andrij

2012-01-01

Upon ATP binding, myosin motor protein is found in two alternative conformations, pre-recovery state M* and post-recovery state M**. The transition from one state to the other, known as the recovery stroke, plays a key role in the myosin functional cycle. Despite much recent research, the microscopic details of this transition remain elusive. A critical step in the recovery stroke is the rotation of the converter domain from “up” position in pre-recovery state to “down” position in post-recovery state that leads to the swing of the lever arm attached to it. In this work, we demonstrate that the two rotational states of the converter domain are determined by the interactions within a small structural motif in the force-generating region of the protein that can be accurately modeled on computers using atomic representation and explicit solvent. Our simulations show that the transition between the two states is controlled by a small helix (SH1) located next to the relay helix and relay loop. A small translation in the position of SH1 away from the relay helix is seen to trigger the transition from “up” state to “down” state. The transition is driven by a cluster of hydrophobic residues I687, F487 and F506 that make significant contributions to the stability of both states. The proposed mechanism agrees well with the available structural and mutational studies. PMID:22855405

Determining effective roadway design treatments for transitioning from rural areas to urban areas on state highways.

DOT National Transportation Integrated Search

2008-09-01

This report reviews an Oregon research effort to identify ways to calm operating speeds as the vehicles transition into developed suburban/urban areas from rural roads. Drivers of vehicles approaching the urban environment have few visual cues to red...

Generalized concurrence in boson sampling.

PubMed

Chin, Seungbeom; Huh, Joonsuk

2018-04-17

A fundamental question in linear optical quantum computing is to understand the origin of the quantum supremacy in the physical system. It is found that the multimode linear optical transition amplitudes are calculated through the permanents of transition operator matrices, which is a hard problem for classical simulations (boson sampling problem). We can understand this problem by considering a quantum measure that directly determines the runtime for computing the transition amplitudes. In this paper, we suggest a quantum measure named "Fock state concurrence sum" C S , which is the summation over all the members of "the generalized Fock state concurrence" (a measure analogous to the generalized concurrences of entanglement and coherence). By introducing generalized algorithms for computing the transition amplitudes of the Fock state boson sampling with an arbitrary number of photons per mode, we show that the minimal classical runtime for all the known algorithms directly depends on C S . Therefore, we can state that the Fock state concurrence sum C S behaves as a collective measure that controls the computational complexity of Fock state BS. We expect that our observation on the role of the Fock state concurrence in the generalized algorithm for permanents would provide a unified viewpoint to interpret the quantum computing power of linear optics.

Equilibration and non-equilibrium steady states in PT-symmetric Toda lattice

NASA Astrophysics Data System (ADS)

Harter, Andrew; Joglekar, Yogesh; Saxena, Avadh

The Toda lattice is a classical discrete integrable model, describing a chain of particles that interact through an exponentially decaying, pairwise potential. It also supports soliton solutions. We consider the fate of this lattice in the presence of localized, spatially separated, balanced drag (loss) and drive (gain). Such systems with balanced gain and loss undergo a transition, the so called parity-time (PT) symmetry breaking transition, from a quasi-equilibrium state to a state that is far removed from equilibrium. We determine the threshold for such a transition in the presence of stochastic and deterministic driving, and study the robustness of our results in the presence of different boundary conditions. This work is supported by DMR-1054020.

Spectroscopy of 50Sc and ab initio calculations of B (M 3 ) strengths

NASA Astrophysics Data System (ADS)

Garnsworthy, A. B.; Bowry, M.; Olaizola, B.; Holt, J. D.; Stroberg, S. R.; Cruz, S.; Georges, S.; Hackman, G.; MacLean, A. D.; Measures, J.; Patel, H. P.; Pearson, C. J.; Svensson, C. E.

2017-10-01

The GRIFFIN spectrometer at TRIUMF-ISAC has been used to study excited states and transitions in 50Sc following the β decay of 50Ca. Branching ratios were determined from the measured γ -ray intensities, and angular correlations of γ rays have been used to firmly assign the spins of excited states. The presence of an isomeric state that decays by an M 3 transition with a B (M 3 ) strength of 13.6(7) W.u. has been confirmed. We compare the first ab initio calculations of B (M 3 ) strengths in light- and medium-mass nuclei from the valence-space in-medium similarity renormalization group approach, using consistently derived effective Hamiltonians and effective M 3 operator. The experimental data are well reproduced for isoscalar M 3 transitions when using bare g factors, but the strength of isovector M 3 transitions are found to be underestimated by an order of magnitude.

Electron affinity and excited states of methylglyoxal

NASA Astrophysics Data System (ADS)

Dauletyarov, Yerbolat; Dixon, Andrew R.; Wallace, Adam A.; Sanov, Andrei

2017-07-01

Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A'), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A' state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A' ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

Sensitivity of peptide conformational dynamics on clustering of a classical molecular dynamics trajectory

NASA Astrophysics Data System (ADS)

Jensen, Christian H.; Nerukh, Dmitry; Glen, Robert C.

2008-03-01

We investigate the sensitivity of a Markov model with states and transition probabilities obtained from clustering a molecular dynamics trajectory. We have examined a 500ns molecular dynamics trajectory of the peptide valine-proline-alanine-leucine in explicit water. The sensitivity is quantified by varying the boundaries of the clusters and investigating the resulting variation in transition probabilities and the average transition time between states. In this way, we represent the effect of clustering using different clustering algorithms. It is found that in terms of the investigated quantities, the peptide dynamics described by the Markov model is sensitive to the clustering; in particular, the average transition times are found to vary up to 46%. Moreover, inclusion of nonphysical sparsely populated clusters can lead to serious errors of up to 814%. In the investigation, the time step used in the transition matrix is determined by the minimum time scale on which the system behaves approximately Markovian. This time step is found to be about 100ps. It is concluded that the description of peptide dynamics with transition matrices should be performed with care, and that using standard clustering algorithms to obtain states and transition probabilities may not always produce reliable results.

Mapping the QCD Phase Transition with Accreting Compact Stars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blaschke, D.; Bogoliubov Laboratory for Theoretical Physics, JINR Dubna, Joliot-Curie str. 6, 141980 Dubna; Poghosyan, G.

2008-10-29

We discuss an idea for how accreting millisecond pulsars could contribute to the understanding of the QCD phase transition in the high-density nuclear matter equation of state (EoS). It is based on two ingredients, the first one being a ''phase diagram'' of rapidly rotating compact star configurations in the plane of spin frequency and mass, determined with state-of-the-art hybrid equations of state, allowing for a transition to color superconducting quark matter. The second is the study of spin-up and accretion evolution in this phase diagram. We show that the quark matter phase transition leads to a characteristic line in themore » {omega}-M plane, the phase border between neutron stars and hybrid stars with a quark matter core. Along this line a drop in the pulsar's moment of inertia entails a waiting point phenomenon in the accreting millisecond pulsar (AMXP) evolution: most of these objects should therefore be found along the phase border in the {omega}-M plane, which may be viewed as the AMXP analog of the main sequence in the Hertzsprung-Russell diagram for normal stars. In order to prove the existence of a high-density phase transition in the cores of compact stars we need population statistics for AMXPs with sufficiently accurate determination of their masses, spin frequencies and magnetic fields.« less

Asymmetric shape transitions of epitaxial quantum dots

PubMed Central

2016-01-01

We construct a two-dimensional continuum model to describe the energetics of shape transitions in fully faceted epitaxial quantum dots (strained islands) via minimization of elastic energy and surface energy at fixed volume. The elastic energy of the island is based on a third-order approximation, enabling us to consider shape transitions between pyramids, domes, multifaceted domes and asymmetric intermediate states. The energetics of the shape transitions are determined by numerically calculating the facet lengths that minimize the energy of a given island type of prescribed island volume. By comparing the energy of different island types with the same volume and analysing the energy surface as a function of the island shape parameters, we determine the bifurcation diagram of equilibrium solutions and their stability, as well as the lowest barrier transition pathway for the island shape as a function of increasing volume. The main result is that the shape transition from pyramid to dome to multifaceted dome occurs through sequential nucleation of facets and involves asymmetric metastable transition shapes. We also explicitly determine the effect of corner energy (facet edge energy) on shape transitions and interpret the results in terms of the relative stability of asymmetric island shapes as observed in experiment. PMID:27436989

Ultrafast X-Ray Diffraction Studies of the Phase Transitions and Equation of State of Scandium Shock Compressed to 82 GPa

DOE PAGES

Briggs, R.; Gorman, M. G.; Coleman, A. L.; ...

2017-01-09

Using x-ray diffraction at the Linac Coherent Light Source x-ray free-electron laser, we have determined simultaneously and self-consistently the phase transitions and equation of state (EOS) of the lightest transition metal, scandium, under shock compression. On compression scandium undergoes a structural phase transition between 32 and 35 GPa to the same bcc structure seen at high temperatures at ambient pressures, and then a further transition at 46 GPa to the incommensurate host-guest polymorph found above 21 GPa in static compression at room temperature. Furthermore, shock melting of the host-guest phase is observed between 53 and 72 GPa with the disappearancemore » of Bragg scattering and the growth of a broad asymmetric diffraction peak from the high-density liquid.« less

Ultrafast X-Ray Diffraction Studies of the Phase Transitions and Equation of State of Scandium Shock Compressed to 82 GPa.

PubMed

Briggs, R; Gorman, M G; Coleman, A L; McWilliams, R S; McBride, E E; McGonegle, D; Wark, J S; Peacock, L; Rothman, S; Macleod, S G; Bolme, C A; Gleason, A E; Collins, G W; Eggert, J H; Fratanduono, D E; Smith, R F; Galtier, E; Granados, E; Lee, H J; Nagler, B; Nam, I; Xing, Z; McMahon, M I

2017-01-13

Using x-ray diffraction at the Linac Coherent Light Source x-ray free-electron laser, we have determined simultaneously and self-consistently the phase transitions and equation of state (EOS) of the lightest transition metal, scandium, under shock compression. On compression scandium undergoes a structural phase transition between 32 and 35 GPa to the same bcc structure seen at high temperatures at ambient pressures, and then a further transition at 46 GPa to the incommensurate host-guest polymorph found above 21 GPa in static compression at room temperature. Shock melting of the host-guest phase is observed between 53 and 72 GPa with the disappearance of Bragg scattering and the growth of a broad asymmetric diffraction peak from the high-density liquid.

Chemical reactions induced by oscillating external fields in weak thermal environments

NASA Astrophysics Data System (ADS)

Craven, Galen T.; Bartsch, Thomas; Hernandez, Rigoberto

2015-02-01

Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead time-dependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the time-varying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates predicted by stability analysis and rates obtained through numerical calculation of the reactive flux. We also show that the optimal dividing surface and the resulting reaction rate for a reactive system driven by weak thermal noise can be approximated well using the transition state geometry of the underlying deterministic system. This agreement persists as long as the thermal driving strength is less than the order of that of the periodic driving. The power of this result is its simplicity. The surprising accuracy of the time-dependent noise-free geometry for obtaining transition state theory rates in chemical reactions driven by periodic fields reveals the dynamics without requiring the cost of brute-force calculations.

Determining effective roadway design treatments for transitioning from rural areas to urban areas on state highways : final report.

DOT National Transportation Integrated Search

2008-09-01

This report reviews an Oregon research effort to identify ways to calm operating speeds as the vehicles transition into developed suburban/urban areas from rural roads. Drivers of vehicles approaching the urban environment have few visual cues to red...

26 CFR 1.337(d)-1 - Transitional loss limitation rule.

Code of Federal Regulations, 2010 CFR

2010-04-01

... value over basis, determined immediately before the transitional subsidiary became a subsidiary, with...) Disposition means any event in which gain or loss is recognized, in whole or in part. (v) Value means fair market value. (5) Examples. For purposes of the examples in this section, unless otherwise stated, the...

Enhancing pairwise state-transition weights: A new weighting scheme in simulated tempering that can minimize transition time between a pair of conformational states

NASA Astrophysics Data System (ADS)

Qiao, Qin; Zhang, Hou-Dao; Huang, Xuhui

2016-04-01

Simulated tempering (ST) is a widely used enhancing sampling method for Molecular Dynamics simulations. As one expanded ensemble method, ST is a combination of canonical ensembles at different temperatures and the acceptance probability of cross-temperature transitions is determined by both the temperature difference and the weights of each temperature. One popular way to obtain the weights is to adopt the free energy of each canonical ensemble, which achieves uniform sampling among temperature space. However, this uniform distribution in temperature space may not be optimal since high temperatures do not always speed up the conformational transitions of interest, as anti-Arrhenius kinetics are prevalent in protein and RNA folding. Here, we propose a new method: Enhancing Pairwise State-transition Weights (EPSW), to obtain the optimal weights by minimizing the round-trip time for transitions among different metastable states at the temperature of interest in ST. The novelty of the EPSW algorithm lies in explicitly considering the kinetics of conformation transitions when optimizing the weights of different temperatures. We further demonstrate the power of EPSW in three different systems: a simple two-temperature model, a two-dimensional model for protein folding with anti-Arrhenius kinetics, and the alanine dipeptide. The results from these three systems showed that the new algorithm can substantially accelerate the transitions between conformational states of interest in the ST expanded ensemble and further facilitate the convergence of thermodynamics compared to the widely used free energy weights. We anticipate that this algorithm is particularly useful for studying functional conformational changes of biological systems where the initial and final states are often known from structural biology experiments.

Enhancing pairwise state-transition weights: A new weighting scheme in simulated tempering that can minimize transition time between a pair of conformational states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao, Qin, E-mail: qqiao@ust.hk; Zhang, Hou-Dao; Huang, Xuhui, E-mail: xuhuihuang@ust.hk

2016-04-21

Simulated tempering (ST) is a widely used enhancing sampling method for Molecular Dynamics simulations. As one expanded ensemble method, ST is a combination of canonical ensembles at different temperatures and the acceptance probability of cross-temperature transitions is determined by both the temperature difference and the weights of each temperature. One popular way to obtain the weights is to adopt the free energy of each canonical ensemble, which achieves uniform sampling among temperature space. However, this uniform distribution in temperature space may not be optimal since high temperatures do not always speed up the conformational transitions of interest, as anti-Arrhenius kineticsmore » are prevalent in protein and RNA folding. Here, we propose a new method: Enhancing Pairwise State-transition Weights (EPSW), to obtain the optimal weights by minimizing the round-trip time for transitions among different metastable states at the temperature of interest in ST. The novelty of the EPSW algorithm lies in explicitly considering the kinetics of conformation transitions when optimizing the weights of different temperatures. We further demonstrate the power of EPSW in three different systems: a simple two-temperature model, a two-dimensional model for protein folding with anti-Arrhenius kinetics, and the alanine dipeptide. The results from these three systems showed that the new algorithm can substantially accelerate the transitions between conformational states of interest in the ST expanded ensemble and further facilitate the convergence of thermodynamics compared to the widely used free energy weights. We anticipate that this algorithm is particularly useful for studying functional conformational changes of biological systems where the initial and final states are often known from structural biology experiments.« less

Modulation of inherent dynamical tendencies of the bisabolyl cation via preorganization in epi-isozizaene synthase.

PubMed

Pemberton, Ryan P; Ho, Krystina C; Tantillo, Dean J

2015-04-01

The relative importance of preorganization, selective transition state stabilization and inherent reactivity are assessed through quantum chemical and docking calculations for a sesquiterpene synthase ( epi -isozizaene synthase, EIZS). Inherent reactivity of the bisabolyl cation, both static and dynamic, appears to determine the pathway to product, although preorganization and selective binding of the final transition state structure in the multi-step carbocation cascade that forms epi -isozizaene appear to play important roles.

Continuum ionization transition probabilities of atomic oxygen

NASA Technical Reports Server (NTRS)

Samson, J. A. R.; Petrosky, V. E.

1974-01-01

The technique of photoelectron spectroscopy was employed in the investigation. Atomic oxygen was produced in a microwave discharge operating at a power of 40 W and at a pressure of approximately 20 mtorr. The photoelectron spectrum of the oxygen with and without the discharge is shown. The atomic states can be clearly seen. In connection with the measurement of the probability for transitions into the various ionic states, the analyzer collection efficiency was determined as a function of electron energy.

E 3 and M 2 transition strengths in Bi20983

NASA Astrophysics Data System (ADS)

Roberts, O. J.; NiÅ£ǎ, C. R.; Bruce, A. M.; Mǎrginean, N.; Bucurescu, D.; Deleanu, D.; Filipescu, D.; Florea, N. M.; Gheorghe, I.; GhiÅ£ǎ, D.; Glodariu, T.; Lica, R.; Mǎrginean, R.; Mihai, C.; Negret, A.; Sava, T.; Stroe, L.; Şuvǎilǎ, R.; Toma, S.; Alharbi, T.; Alexander, T.; Aydin, S.; Brown, B. A.; Browne, F.; Carroll, R. J.; Mulholland, K.; Podolyák, Zs.; Regan, P. H.; Smith, J. F.; Smolen, M.; Townsley, C. M.

2016-01-01

The 1 i13/2→1 h9/2 (M 2 ) and 3 s1/2→2 f7/2 (E 3 ) reduced proton transition probabilities in Bi20983 have been determined from the direct half-life measurements of the 13/21+ and 1/21+ states using the Romanian array for γ -ray SPectroscopy in HEavy ion REactions (RoSPHERE). The 13/21+ and 1/21+ states were found to have T1/2=0.120 (15 ) ns and T1/2=9.02 (24 ) ns respectively. Angular distribution measurements were used to determine an E 3 /M 2 mixing ratio of δ =-0.184 (13 ) for the 1609 keV γ -ray transition deexciting the 13/21+ state. This value for δ was combined with the measured half-life to give reduced transition probabilities of B (E 3 ,13/21+→9/21-) =12 (2 ) ×103 e2fm6 and B (M 2 ,13/21+→9/21-) =38 (5 ) μN2fm2 . These values are in good agreement with calculations within the finite Fermi system. The extracted value of B (E 3 ,1/21+→7/21-) =6.3 (2 ) ×103 e2fm6 can be explained by a small (˜6 % ) admixture in the wave function of the 1/21+ state.

A Search for Transitions between States in Redbacks and Black Widows Using Seven Years of Fermi -LAT Observations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torres, Diego F.; Li, Jian; Rea, Nanda

Considering about seven years of Fermi -Large Area Telescope (LAT) data, we present a systematic search for variability that is possibly related to transitions between states in redbacks and black widow systems. The transitions are characterized by sudden and significant changes in the gamma-ray flux that persist on a timescale that is much larger than the orbital period. This phenomenology was already detected in the case of two redback systems, PSR J1023+0038 and PSR J1227−4853, which we present here. We show the existence of only one transition for each of these systems over the past seven years. We determine theirmore » spectra, establishing high-energy cutoffs at a few GeV for the high gamma-ray state of PSR J1023+0038, and for both states of PSR J1227−4853. The surveying capability of the Fermi -LAT allows further study of whether similar phenomenology has occurred in other sources. Although we have not found any evidence of a state transition for most of the studied pulsars, we note two black-widow systems, PSR J2234+0944 and PSR J1446−4701, whose apparent variabilities are reminiscent of the transitions in PSR J1023+0038 and PSR J1227−4853. For the other systems, we set limits on potential transitions in their measured gamma-ray light curves.« less

Polarized two-photon photoselection in EGFP: Theory and experiment

NASA Astrophysics Data System (ADS)

Masters, T. A.; Marsh, R. J.; Blacker, T. S.; Armoogum, D. A.; Larijani, B.; Bain, A. J.

2018-04-01

In this work, we present a complete theoretical description of the excited state order created by two-photon photoselection from an isotropic ground state; this encompasses both the conventionally measured quadrupolar (K = 2) and the "hidden" degree of hexadecapolar (K = 4) transition dipole alignment, their dependence on the two-photon transition tensor and emission transition dipole moment orientation. Linearly and circularly polarized two-photon absorption (TPA) and time-resolved single- and two-photon fluorescence anisotropy measurements are used to determine the structure of the transition tensor in the deprotonated form of enhanced green fluorescent protein. For excitation wavelengths between 800 nm and 900 nm, TPA is best described by a single element, almost completely diagonal, two-dimensional (planar) transition tensor whose principal axis is collinear to that of the single-photon S0 → S1 transition moment. These observations are in accordance with assignments of the near-infrared two-photon absorption band in fluorescent proteins to a vibronically enhanced S0 → S1 transition.

Polarized two-photon photoselection in EGFP: Theory and experiment.

PubMed

Masters, T A; Marsh, R J; Blacker, T S; Armoogum, D A; Larijani, B; Bain, A J

2018-04-07

In this work, we present a complete theoretical description of the excited state order created by two-photon photoselection from an isotropic ground state; this encompasses both the conventionally measured quadrupolar (K = 2) and the "hidden" degree of hexadecapolar (K = 4) transition dipole alignment, their dependence on the two-photon transition tensor and emission transition dipole moment orientation. Linearly and circularly polarized two-photon absorption (TPA) and time-resolved single- and two-photon fluorescence anisotropy measurements are used to determine the structure of the transition tensor in the deprotonated form of enhanced green fluorescent protein. For excitation wavelengths between 800 nm and 900 nm, TPA is best described by a single element, almost completely diagonal, two-dimensional (planar) transition tensor whose principal axis is collinear to that of the single-photon S 0 → S 1 transition moment. These observations are in accordance with assignments of the near-infrared two-photon absorption band in fluorescent proteins to a vibronically enhanced S 0 → S 1 transition.

Ground-state ordering of the J1-J2 model on the simple cubic and body-centered cubic lattices

NASA Astrophysics Data System (ADS)

Farnell, D. J. J.; Götze, O.; Richter, J.

2016-06-01

The J1-J2 Heisenberg model is a "canonical" model in the field of quantum magnetism in order to study the interplay between frustration and quantum fluctuations as well as quantum phase transitions driven by frustration. Here we apply the coupled cluster method (CCM) to study the spin-half J1-J2 model with antiferromagnetic nearest-neighbor bonds J1>0 and next-nearest-neighbor bonds J2>0 for the simple cubic (sc) and body-centered cubic (bcc) lattices. In particular, we wish to study the ground-state ordering of these systems as a function of the frustration parameter p =z2J2/z1J1 , where z1 (z2) is the number of nearest (next-nearest) neighbors. We wish to determine the positions of the phase transitions using the CCM and we aim to resolve the nature of the phase transition points. We consider the ground-state energy, order parameters, spin-spin correlation functions, as well as the spin stiffness in order to determine the ground-state phase diagrams of these models. We find a direct first-order phase transition at a value of p =0.528 from a state of nearest-neighbor Néel order to next-nearest-neighbor Néel order for the bcc lattice. For the sc lattice the situation is more subtle. CCM results for the energy, the order parameter, the spin-spin correlation functions, and the spin stiffness indicate that there is no direct first-order transition between ground-state phases with magnetic long-range order, rather it is more likely that two phases with antiferromagnetic long range are separated by a narrow region of a spin-liquid-like quantum phase around p =0.55 . Thus the strong frustration present in the J1-J2 Heisenberg model on the sc lattice may open a window for an unconventional quantum ground state in this three-dimensional spin model.

Variational calculation of macrostate transition rates

NASA Astrophysics Data System (ADS)

Ulitsky, Alex; Shalloway, David

1998-08-01

We develop the macrostate variational method (MVM) for computing reaction rates of diffusive conformational transitions in multidimensional systems by a variational coarse-grained "macrostate" decomposition of the Smoluchowski equation. MVM uses multidimensional Gaussian packets to identify and focus computational effort on the "transition region," a localized, self-consistently determined region in conformational space positioned roughly between the macrostates. It also determines the "transition direction" which optimally specifies the projected potential of mean force for mean first-passage time calculations. MVM is complementary to variational transition state theory in that it can efficiently solve multidimensional problems but does not accommodate memory-friction effects. It has been tested on model 1- and 2-dimensional potentials and on the 12-dimensional conformational transition between the isoforms of a microcluster of six-atoms having only van der Waals interactions. Comparison with Brownian dynamics calculations shows that MVM obtains equivalent results at a fraction of the computational cost.

MICROWAVE SPECTROSCOPY OF THE CALCIUM 4snf→4s(n+1)d, 4sng, 4snh, 4sni, AND 4snk TRANSITIONS

NASA Astrophysics Data System (ADS)

Nunkaew, Jirakan; Gallagher, Tom

2015-06-01

We use a delayed field ionization technique to observe the microwave transitions of calcium Rydberg states, from the 4snf states to the 4s(n+1)d, 4sng, 4snh, 4sni, and 4snk states for 18≤ n≤23. We analyze the observed intervals between the ℓ and (ℓ+1), ℓ≥5, states of the same n to determine the Ca^+ 4s dipole and quadrupole polarizabilities. We show that the adiabatic core polarization model is not adequate to extract the Ca^+ 4s dipole and quadrupole polarizabilities and a non adiabatic treatment is required. We use the non adiabatic core polarization model to determine the ionic dipole and quadrupole polarizabilities to be α_d=76.9(3);a_0^3 and α_q=206(9);a_0^5, respectively.

Markov-chain model of classified atomistic transition states for discrete kinetic Monte Carlo simulations.

PubMed

Numazawa, Satoshi; Smith, Roger

2011-10-01

Classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The scheme is then used to determine transitions that can be applied in a lattice-based kinetic Monte Carlo (KMC) atomistic simulation model. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multidimensional Boolean valued functions in three-dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology-dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. Excellent agreement with observed experimental results is obtained.

Exploring extensions to multi-state models with multiple unobservable states

USGS Publications Warehouse

Bailey, L.L.; Kendall, W.L.; Church, D.R.; Thomson, David L.; Cooch, Evan G.; Conroy, Michael J.

2009-01-01

Many biological systems include a portion of the target population that is unobservable during certain life history stages. Transition to and from an unobservable state may be of primary interest in many ecological studies and such movements are easily incorporated into multi-state models. Several authors have investigated properties of open-population multi-state mark-recapture models with unobservable states, and determined the scope and constraints under which parameters are identifiable (or, conversely, are redundant), but only in the context of a single observable and a single unobservable state (Schmidt et al. 2002; Kendall and Nichols 2002; Schaub et al. 2004; Kendall 2004). Some of these constraints can be relaxed if data are collected under a version of the robust design (Kendall and Bjorkland 2001; Kendall and Nichols 2002; Kendall 2004; Bailey et al. 2004), which entails >1 capture period per primary period of interest (e.g., 2 sampling periods within a breeding season). The critical assumption shared by all versions of the robust design is that the state of the individual (e.g. observable or unobservable) remains static for the duration of the primary period (Kendall 2004). In this paper, we extend previous work by relaxing this assumption to allow movement among observable states within primary periods while maintaining static observable or unobservable states. Stated otherwise, both demographic and geographic closure assumptions are relaxed, but all individuals are either observable or unobservable within primary periods. Within these primary periods transitions are possible among multiple observable states, but transitions are not allowed among the corresponding unobservable states. Our motivation for this work is exploring potential differences in population parameters for pond-breeding amphibians, where the quality of habitat surrounding the pond is not spatially uniform. The scenario is an example of a more general case where individuals move between habitats both during the breeding season (within primary periods; transitions among observable states only) and during the non-breeding season (between primary periods; transitions between observable and unobservable states). Presumably, habitat quality affects demographic parameters (e.g. survival and breeding probabilities). Using this model we are able to test this prediction for amphibians and determine if individuals move to more favorable habitats to increase survival and breeding probabilities.

Highly excited symmetry-breaking infrared and THz transitions in methanol-D 1

NASA Astrophysics Data System (ADS)

Mukhopadhyay, Indranath

2004-06-01

In this paper, symmetry-breaking transitions have been identified in the Fourier transform infrared (FTIR) and Terra Hertz (THz) fast scan spectra of asymmetrically deuterated methanol CH 2DOH involving three quanta of the lowest lying vibrational state ( ν1). These transitions have an upper state belonging to highly excited torsional state with the torsional quantum number v=11 (e 5) (with the axial component of total rotational angular momentum K=5 and 6) in the Internal Axis Method (IAM) formalism developed by Quade and his co-workers [J. Mol. Spectrosc. 146 (1991) 238; J. Mol. Spectrosc. 146 (1991) 252], which was later extended by Mukhopadhyay [Spectrochim. Acta A 53 (1997) 2457; Spectrochim. Acta A 53 (1997) 1947] to include highly excited torsional-rotational states. The originating lower states belong to the o 1 ( v=3) with K=4 and 5. In analogy with pure methanol these transitions terminate to the third excited torsional state, which has very small torsional matrix elements to be observable in normal FTIR spectra. The location of the e 5 states suggests that the calculated energy levels using the parameters of Liu and Quade [J. Mol. Spectrosc. 146 (1991) 252] are reasonable and very helpful to assign such highly excited transitions, considering that their studies include low angular momentum states. In addition the very existence of these transitions proves that the matrix elements calculated by Mukhopadhyay [Spectrochim. Acta A 53 (1997) 1947] are very useful and dependable. Thus they represent a valuable tool for entangling the complex spectrum of this asymmetrically deuterated methanol. In order to provide confirmatory evidence the THz spectra obtained using the Fast Scanning Submillimeter Spectroscopy Technique (FASSST) at the Ohio State University [Rev. Instr. 68 (1997) 1675; Anal. Chem. 70 (1998) 719A] were searched for the ground state transitions that can be calculated precisely from IR combination relations. All the transitions that can be predicted with K=4 and 5 in the o 1 states are indeed identified in the FASSST spectrum. To our knowledge this is the first reported work involving direct transitions to such highly excited torsional state of CH 2DOH. This work will enable the determination of higher order barrier terms and provide enough understanding of the energy levels for the identification of many unidentified transitions. To our knowledge, this is the first time such high frequency symmetry-breaking transitions have been observed in asymmetrically deuterated methanol.

General magnetic transition dipole moments for electron paramagnetic resonance.

PubMed

Nehrkorn, Joscha; Schnegg, Alexander; Holldack, Karsten; Stoll, Stefan

2015-01-09

We present general expressions for the magnetic transition rates in electron paramagnetic resonance (EPR) experiments of anisotropic spin systems in the solid state. The expressions apply to general spin centers and arbitrary excitation geometry (Voigt, Faraday, and intermediate). They work for linear and circular polarized as well as unpolarized excitation, and for crystals and powders. The expressions are based on the concept of the (complex) magnetic transition dipole moment vector. Using the new theory, we determine the parities of ground and excited spin states of high-spin (S=5/2) Fe(III) in hemin from the polarization dependence of experimental EPR line intensities.

MHD Simulation for Investigating the Dynamic State Transition Responsible for a Solar Eruption in Active Region 12158

NASA Astrophysics Data System (ADS)

Lee, Hwanhee; Magara, Tetsuya

2018-06-01

We present a magnetohydrodynamic model of solar eruption based on the dynamic state transition from the quasi-static state to the eruptive state of an active region (AR) magnetic field. For the quasi-static state before an eruption, we consider the existence of a slow solar wind originating from an AR, which may continuously make the AR magnetic field deviate from mechanical equilibrium. In this model, we perform a three-dimensional magnetohydrodynamic simulation of AR 12158 producing a coronal mass ejection, where the initial magnetic structure of the simulation is given by a nonlinear force-free field derived from an observed photospheric vector magnetic field. We then apply a pressure-driven outflow to the upper part of the magnetic structure to achieve a quasi-static pre-eruptive state. The simulation shows that the eruptive process observed in this AR may be caused by the dynamic state transition of an AR magnetic field, which is essentially different from the destabilization of a static magnetic field. The dynamic state transition is determined from the shape evolution of the magnetic field line according to the κH-mechanism. This work demonstrates how the mechanism works to produce a solar eruption in the dynamic solar corona governed by the gravitational field and the continuous outflows of solar wind.

Shape coexistence and evolution in 98Sr

NASA Astrophysics Data System (ADS)

Park, J.; Garnsworthy, A. B.; Krücken, R.; Andreoiu, C.; Ball, G. C.; Bender, P. C.; Chester, A.; Close, A.; Finlay, P.; Garrett, P. E.; Glister, J.; Hackman, G.; Hadinia, B.; Leach, K. G.; Rand, E. T.; Sjue, S.; Starosta, K.; Svensson, C. E.; Tardiff, E.

2016-01-01

Shape coexistence between the strongly deformed ground state and the weakly deformed 02+ state in 98Sr has been a major topic of interest due to the energy difference of 215 keV, which is the smallest in all even-even nuclei. The electric monopole transition strength ρ2(E 0 ) is an important quantity that can relate the deformation difference and the shape mixing between the two 0+ states, which are admixtures of the vibrational (S) and the rotational (D) states in a simple mixing model. In a β -decay spectroscopy experiment, the experimental ρ2(E 0 ) was measured. A value of 0.053(5) is consistent with the previous measurement and was combined with known electric quadrupole transition strengths B (E 2 ) in calculations of a two-state mixing model. Based on a systematic study on neighboring Kr, Zr, and Mo isotopes, the mixing of the 0+ and 2+ states in 98Sr was determined to be 8.6% and 1.3%, respectively, corresponding to deformation parameters βD=0.38 (1 ) and βS=-0.23 (2 ) . These parameters reproduce experimental transition strengths well except for the 41+→21+ transition, which suggests a smaller D-band deformation for J ≥4 .

Electronic spectroscopy of diatomic molecules

NASA Technical Reports Server (NTRS)

Partridge, Harry; Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.

1994-01-01

This article provides an overview of the principal computational approaches and their accuracy for the study of electronic spectroscopy of diatomic molecules. We include a number of examples from our work that illustrate the range of application. We show how full configuration interaction benchmark calculations were instrumental in improving the understanding of the computational requirements for obtaining accurate results for diatomic spectroscopy. With this understanding it is now possible to compute radiative lifetimes accurate to within 10% for systems involving first- and second-row atoms. We consider the determination of the infrared vibrational transition probabilities for the ground states of SiO and NO, based on a globally accurate dipole moment function. We show how we were able to assign the a(sup "5)II state of CO as the upper state in the recently observed emission bands of CO in an Ar matrix. We next discuss the assignment of the photoelectron detachment spectra of NO and the alkali oxide negative ions. We then present several examples illustrating the state-of-the-art in determining radiative lifetimes for valence-valence and valence-Rydberg transitions. We next compare the molecular spectroscopy of the valence isoelectronic B2, Al2, and AlB molecules. The final examples consider systems involving transition metal atoms, which illustrate the difficulty in describing states with different numbers of d electrons.

Determining the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose using an automatic water vapor sorption instrument.

PubMed

Yuan, Xiaoda; Carter, Brady P; Schmidt, Shelly J

2011-01-01

Similar to an increase in temperature at constant moisture content, water vapor sorption by an amorphous glassy material at constant temperature causes the material to transition into the rubbery state. However, comparatively little research has investigated the measurement of the critical relative humidity (RHc) at which the glass transition occurs at constant temperature. Thus, the central objective of this study was to investigate the relationship between the glass transition temperature (Tg), determined using thermal methods, and the RHc obtained using an automatic water vapor sorption instrument. Dynamic dewpoint isotherms were obtained for amorphous polydextrose from 15 to 40 °C. RHc was determined using an optimized 2nd-derivative method; however, 2 simpler RHc determination methods were also tested as a secondary objective. No statistical difference was found between the 3 RHc methods. Differential scanning calorimetry (DSC) Tg values were determined using polydextrose equilibrated from 11.3% to 57.6% RH. Both standard DSC and modulated DSC (MDSC) methods were employed, since some of the polydextrose thermograms exhibited a physical aging peak. Thus, a tertiary objective was to compare Tg values obtained using 3 different methods (DSC first scan, DSC rescan, and MDSC), to determine which method(s) yielded the most accurate Tg values. In general, onset and midpoint DSC first scan and MDSC Tg values were similar, whereas onset and midpoint DSC rescan values were different. State diagrams of RHc and experimental temperature and Tg and %RH were compared. These state diagrams, though obtained via very different methods, showed relatively good agreement, confirming our hypothesis that water vapor sorption isotherms can be used to directly detect the glassy to rubbery transition. Practical Application: The food polymer science (FPS) approach, pioneered by Slade and Levine, is being successfully applied in the food industry for understanding, improving, and developing food processes and products. However, despite its extreme usefulness, the Tg, a key element of the FPS approach, remains a challenging parameter to routinely measure in amorphous food materials, especially complex materials. This research demonstrates that RHc values, obtained at constant temperature using an automatic water vapor sorption instrument, can be used to detect the glassy to rubbery transition and are similar to the Tg values obtained at constant %RH, especially considering the very different approaches of these 2 methods--a transition from surface adsorption to bulk absorption (water vapor sorption) versus a step change in the heat capacity (DSC thermal method).

Threshold of coexistence and critical behavior of a predator-prey stochastic model in a fractal landscape

NASA Astrophysics Data System (ADS)

Argolo, C.; Barros, P.; Tomé, T.; Arashiro, E.; Gleria, Iram; Lyra, M. L.

2016-08-01

We investigate a stochastic lattice model describing a predator-prey system in a fractal scale-free landscape, mimicked by the fractal Sierpinski carpet. We determine the threshold of species coexistence, that is, the critical phase boundary related to the transition between an active state, where both species coexist and an absorbing state where one of the species is extinct. We show that the predators must live longer in order to persist in a fractal habitat. We further performed a finite-size scaling analysis in the vicinity of the absorbing-state phase transition to compute a set of stationary and dynamical critical exponents. Our results indicate that the transition belongs to the directed percolation universality class exhibited by the usual contact process model on the same fractal landscape.

Enzymatic Transition States, Transition-State Analogs, Dynamics, Thermodynamics, and Lifetimes

PubMed Central

Schramm, Vern L.

2017-01-01

Experimental analysis of enzymatic transition-state structures uses kinetic isotope effects (KIEs) to report on bonding and geometry differences between reactants and the transition state. Computational correlation of experimental values with chemical models permits three-dimensional geometric and electrostatic assignment of transition states formed at enzymatic catalytic sites. The combination of experimental and computational access to transition-state information permits (a) the design of transition-state analogs as powerful enzymatic inhibitors, (b) exploration of protein features linked to transition-state structure, (c) analysis of ensemble atomic motions involved in achieving the transition state, (d) transition-state lifetimes, and (e) separation of ground-state (Michaelis complexes) from transition-state effects. Transition-state analogs with picomolar dissociation constants have been achieved for several enzymatic targets. Transition states of closely related isozymes indicate that the protein’s dynamic architecture is linked to transition-state structure. Fast dynamic motions in catalytic sites are linked to transition-state generation. Enzymatic transition states have lifetimes of femtoseconds, the lifetime of bond vibrations. Binding isotope effects (BIEs) reveal relative reactant and transition-state analog binding distortion for comparison with actual transition states. PMID:21675920

Study of ground state optical transfer for ultracold alkali dimers

NASA Astrophysics Data System (ADS)

Bouloufa-Maafa, Nadia; Londono, Beatriz; Borsalino, Dimitri; Vexiau, Romain; Mahecha, Jorge; Dulieu, Olivier; Luc-Koenig, Eliane

2013-05-01

Control of molecular states by laser pulses offer promising potential applications. The manipulation of molecules by external fields requires precise knowledge of the molecular structure. Our motivation is to perform a detailed analysis of the spectroscopic properties of alkali dimers, with the aim to determine efficient optical paths to form molecules in the absolute ground state and to determine the optimal parameters of the optical lattices where those molecules are manipulated to avoid losses by collisions. To this end, we use state of the art molecular potentials, R-dependent spin-orbit coupling and transition dipole moment to perform our calculations. R-dependent SO coupling are of crucial importance because the transitions occur at internuclear distances where they are affected by this R-dependence. Efficient schemes to transfer RbCs, KRb and KCs to the absolute ground state as well as the optimal parameters of the optical lattices will be presented. This work was supported in part by ``Triangle de la Physique'' under contract 2008-007T-QCCM (Quantum Control of Cold Molecules).

Otx2 is an intrinsic determinant of the embryonic stem cell state and is required for transition to a stable epiblast stem cell condition.

PubMed

Acampora, Dario; Di Giovannantonio, Luca G; Simeone, Antonio

2013-01-01

Mouse embryonic stem cells (ESCs) represent the naïve ground state of the preimplantation epiblast and epiblast stem cells (EpiSCs) represent the primed state of the postimplantation epiblast. Studies have revealed that the ESC state is maintained by a dynamic mechanism characterized by cell-to-cell spontaneous and reversible differences in sensitivity to self-renewal and susceptibility to differentiation. This metastable condition ensures indefinite self-renewal and, at the same time, predisposes ESCs for differentiation to EpiSCs. Despite considerable advances, the molecular mechanism controlling the ESC state and pluripotency transition from ESCs to EpiSCs have not been fully elucidated. Here we show that Otx2, a transcription factor essential for brain development, plays a crucial role in ESCs and EpiSCs. Otx2 is required to maintain the ESC metastable state by antagonizing ground state pluripotency and promoting commitment to differentiation. Furthermore, Otx2 is required for ESC transition into EpiSCs and, subsequently, to stabilize the EpiSC state by suppressing, in pluripotent cells, the mesendoderm-to-neural fate switch in cooperation with BMP4 and Fgf2. However, according to its central role in neural development and differentiation, Otx2 is crucially required for the specification of ESC-derived neural precursors fated to generate telencephalic and mesencephalic neurons. We propose that Otx2 is a novel intrinsic determinant controlling the functional integrity of ESCs and EpiSCs.

Fixed and equilibrium endpoint problems in uneven-aged stand management

Treesearch

Robert G. Haight; Wayne M. Getz

1987-01-01

Studies in uneven-aged management have concentrated on the determination of optimal steady-state diameter distribution harvest policies for single and mixed species stands. To find optimal transition harvests for irregular stands, either fixed endpoint or equilibrium endpoint constraints can be imposed after finite transition periods. Penalty function and gradient...

The Impact of an Immersion Program for Newcomers on the Transitional Period

ERIC Educational Resources Information Center

Rivera, Carmen Iris

2009-01-01

This evaluative dissertation was designed to determine how an immersion program for newcomer students affects their transitional period upon entering the school system. A key element of the study investigated the connection between the emotional state of mind of newcomer students and academic achievement. Both qualitative and quantitative…

Characterization of biomaterials using FT-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Söderholm, S.; Roos, Y. H.; Meinander, N.; Hotokka, M.

1998-06-01

Carbohydrates play an important role in the quality and preservation of pharmaceutical and food materials. The storage temperature and water content is very critical in storage and, therefore, it is very important to understand how the physical state of carbohydrates is affected by water. Carbohydrates in foods and pharmaceuticals are usually present in the amorphous form even if other substances present affect the physical properties of carbohydrates it is mainly temperature and water content that determine the physical state. Amorphous carbohydrates show a second order phase transition, the glass transition, that is critical for stability. When carbohydrates are stored above their glass transition temperature they loose stability. Crystallization above the glass transition temperature may result in loss of quality. Raman spectroscopy offers a useful tool in the characterization of phase transitions and effects of temperature and water content on material properties at a molecular level.

Possible observation of the Berezinskii-Kosterlitz-Thouless transition in boron-doped diamond films

NASA Astrophysics Data System (ADS)

Coleman, Christopher; Bhattacharyya, Somnath

2017-11-01

The occurrence of the Berezinskii-Kosterlitz-Thouless (BKT) transition is investigated in heavily boron-doped nanocrystalline diamond films through a combination of current-voltage and resistance measurements. We observe transport features suggesting a robust BKT transition along with transport features related to vortex pinning in nanocrystalline diamond films with smaller grain size. The vortex core energy determined through analysis of the resistance temperature curves was found to be anti-correlated to the BKT transition temperatures. It is also observed that the higher BKT temperature is related to an increased vortex-antivortex binding energy derived from the activated transport regions. Further, the magnetic field induced superconductor insulator transition shows the possibility of the charge glass state. The consequences of granularity such as localization and vortex pinning can lead to tuneable BKT temperatures and strongly affects the field induced insulating state.

Kinetic or Dynamic Control on a Bifurcating Potential Energy Surface? An Experimental and DFT Study of Gold-Catalyzed Ring Expansion and Spirocyclization of 2-Propargyl-β-tetrahydrocarbolines.

PubMed

Zhang, Lei; Wang, Yi; Yao, Zhu-Jun; Wang, Shaozhong; Yu, Zhi-Xiang

2015-10-21

In classical transition state theory, a transition state is connected to its reactant(s) and product(s). Recently, chemists found that reaction pathways may bifurcate after a transition state, leading to two or more sets of products. The product distribution for such a reaction containing a bifurcating potential energy surface (bPES) is usually determined by the shape of the bPES and dynamic factors. However, if the bPES leads to two intermediates (other than two products), which then undergo further transformations to give different final products, what factors control the selectivity is still not fully examined. This missing link in transition state theory is founded in the present study. Aiming to develop new methods for the synthesis of azocinoindole derivatives, we found that 2-propargyl-β-tetrahydrocarbolines can undergo ring expansion and spirocyclization under gold catalysis. DFT study revealed that the reaction starts with the intramolecular cyclization of the gold-activated 2-propargyl-β-tetrahydrocarboline with a bPES. The cyclization intermediates can not only interconvert into each other via a [1,5]-alkenyl shift, but also undergo ring expansion (through fragmentation/protodeauration mechanism) or spirocyclization (through deprotonation/protodeauration mechanism). Detailed analysis of the complex PESs for substrates with different substituents indicated that the reaction selectivity is under dynamic control if the interconversion of the intermediates is slower than the ring expansion and spirocyclization processes. Otherwise, the chemical outcome is under typical kinetic control and determined by the relative preference of ring expansion versus spirocyclization pathways. The present study may enrich chemist's understanding of the determinants for selectivities on bPESs.

Landscape approaches for determining the ensemble of folding transition states: Success and failure hinge on the degree of frustration

NASA Astrophysics Data System (ADS)

Nymeyer, Hugh; Socci, Nicholas D.; Onuchic, José Nelson

2000-01-01

* Department of Physics, University of California at San Diego, La Jolla, CA 92093-0319; and § Center for Studies in Physics and Biology, The Rockefeller University, New York, NY 10021 Edited by R. Stephen Berry, University of Chicago, Chicago, IL, and approved November 5, 1999 (received for review July 2, 1999) We present a method for determining structural properties of the ensemble of folding transition states from protein simulations. This method relies on thermodynamic quantities (free energies as a function of global reaction coordinates, such as the percentage of native contacts) and not on "kinetic" measurements (rates, transmission coefficients, complete trajectories); consequently, it requires fewer computational resources compared with otherapproaches, making it more suited to large and complex models. We explain the theoretical framework that underlies this method and use it to clarify the connection between the experimentally determined value, a quantity determined by the ratio of rate and stability changes due to point mutations, and the average structure of the transition state ensemble. To determine the accuracy of this thermodynamic approach, we apply it to minimalist protein models and compare these results with the ones obtained by using the standard experimental procedure for determining values. We show that the accuracy of both methods depends sensitively on the amount of frustration. In particular, the results are similar when applied to models with minimal amounts of frustration, characteristic of rapid-folding, single-domain globular proteins.

Modeling personnel turnover in the parametric organization

NASA Technical Reports Server (NTRS)

Dean, Edwin B.

1991-01-01

A model is developed for simulating the dynamics of a newly formed organization, credible during all phases of organizational development. The model development process is broken down into the activities of determining the tasks required for parametric cost analysis (PCA), determining the skills required for each PCA task, determining the skills available in the applicant marketplace, determining the structure of the model, implementing the model, and testing it. The model, parameterized by the likelihood of job function transition, has demonstrated by the capability to represent the transition of personnel across functional boundaries within a parametric organization using a linear dynamical system, and the ability to predict required staffing profiles to meet functional needs at the desired time. The model can be extended by revisions of the state and transition structure to provide refinements in functional definition for the parametric and extended organization.

Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

Raju, Muralikrishna; Banuti, Daniel T; Ma, Peter C; Ihme, Matthias

2017-06-08

Recent experiments on pure fluids have identified distinct liquid-like and gas-like regimes even under supercritical conditions. The supercritical liquid-gas transition is marked by maxima in response functions that define a line emanating from the critical point, referred to as Widom line. However, the structure of analogous state transitions in mixtures of supercritical fluids has not been determined, and it is not clear whether a Widom line can be identified for binary mixtures. Here, we present first evidence for the existence of multiple Widom lines in binary mixtures from molecular dynamics simulations. By considering mixtures of noble gases, we show that, depending on the phase behavior, mixtures transition from a liquid-like to a gas-like regime via distinctly different pathways, leading to phase relationships of surprising complexity and variety. Specifically, we show that miscible binary mixtures have behavior analogous to a pure fluid and the supercritical state space is characterized by a single liquid-gas transition. In contrast, immiscible binary mixture undergo a phase separation in which the clusters transition separately at different temperatures, resulting in multiple distinct Widom lines. The presence of this unique transition behavior emphasizes the complexity of the supercritical state to be expected in high-order mixtures of practical relevance.

Lifetime measurement of neutron-rich even-even molybdenum isotopes

NASA Astrophysics Data System (ADS)

Ralet, D.; Pietri, S.; Rodríguez, T.; Alaqeel, M.; Alexander, T.; Alkhomashi, N.; Ameil, F.; Arici, T.; Ataç, A.; Avigo, R.; Bäck, T.; Bazzacco, D.; Birkenbach, B.; Boutachkov, P.; Bruyneel, B.; Bruce, A. M.; Camera, F.; Cederwall, B.; Ceruti, S.; Clément, E.; Cortés, M. L.; Curien, D.; De Angelis, G.; Désesquelles, P.; Dewald, M.; Didierjean, F.; Domingo-Pardo, C.; Doncel, M.; Duchêne, G.; Eberth, J.; Gadea, A.; Gerl, J.; Ghazi Moradi, F.; Geissel, H.; Goigoux, T.; Goel, N.; Golubev, P.; González, V.; Górska, M.; Gottardo, A.; Gregor, E.; Guastalla, G.; Givechev, A.; Habermann, T.; Hackstein, M.; Harkness-Brennan, L.; Henning, G.; Hess, H.; Hüyük, T.; Jolie, J.; Judson, D. S.; Jungclaus, A.; Knoebel, R.; Kojouharov, I.; Korichi, A.; Korten, W.; Kurz, N.; Labiche, M.; Lalović, N.; Louchart-Henning, C.; Mengoni, D.; Merchán, E.; Million, B.; Morales, A. I.; Napoli, D.; Naqvi, F.; Nyberg, J.; Pietralla, N.; Podolyák, Zs.; Pullia, A.; Prochazka, A.; Quintana, B.; Rainovski, G.; Reese, M.; Recchia, F.; Reiter, P.; Rudolph, D.; Salsac, M. D.; Sanchis, E.; Sarmiento, L. G.; Schaffner, H.; Scheidenberger, C.; Sengele, L.; Singh, B. S. Nara; Singh, P. P.; Stahl, C.; Stezowski, O.; Thoele, P.; Valiente Dobon, J. J.; Weick, H.; Wendt, A.; Wieland, O.; Winfield, J. S.; Wollersheim, H. J.; Zielinska, M.; PreSPEC Collaboration

2017-03-01

Background: In the neutron-rich A ≈100 mass region, rapid shape changes as a function of nucleon number as well as coexistence of prolate, oblate, and triaxial shapes are predicted by various theoretical models. Lifetime measurements of excited levels in the molybdenum isotopes allow the determination of transitional quadrupole moments, which in turn provides structural information regarding the predicted shape change. Purpose: The present paper reports on the experimental setup, the method that allowed one to measure the lifetimes of excited states in even-even molybdenum isotopes from mass A =100 up to mass A =108 , and the results that were obtained. Method: The isotopes of interest were populated by secondary knock-out reaction of neutron-rich nuclei separated and identified by the GSI fragment separator at relativistic beam energies and detected by the sensitive PreSPEC-AGATA experimental setup. The latter included the Lund-York-Cologne calorimeter for identification, tracking, and velocity measurement of ejectiles, and AGATA, an array of position sensitive segmented HPGe detectors, used to determine the interaction positions of the γ ray enabling a precise Doppler correction. The lifetimes were determined with a relativistic version of the Doppler-shift-attenuation method using the systematic shift of the energy after Doppler correction of a γ -ray transition with a known energy. This relativistic Doppler-shift-attenuation method allowed the determination of mean lifetimes from 2 to 250 ps. Results: Even-even molybdenum isotopes from mass A =100 to A =108 were studied. The decays of the low-lying states in the ground-state band were observed. In particular, two mean lifetimes were measured for the first time: τ =29 .7-9.1+11.3 ps for the 4+ state of 108Mo and τ =3 .2-0.7+0.7 ps for the 6+ state of 102Mo. Conclusions: The reduced transition strengths B (E 2 ) , calculated from lifetimes measured in this experiment, compared to beyond-mean-field calculations, indicate a gradual shape transition in the chain of molybdenum isotopes when going from A =100 to A =108 with a maximum reached at N =64 . The transition probabilities decrease for 108Mo which may be related to its well-pronounced triaxial shape indicated by the calculations.

Transition from amplitude to oscillation death in a network of oscillators

NASA Astrophysics Data System (ADS)

Nandan, Mauparna; Hens, C. R.; Pal, Pinaki; Dana, Syamal K.

2014-12-01

We report a transition from a homogeneous steady state (HSS) to inhomogeneous steady states (IHSSs) in a network of globally coupled identical oscillators. We perturb a synchronized population of oscillators in the network with a few local negative or repulsive mean field links. The whole population splits into two clusters for a certain number of repulsive mean field links and a range of coupling strength. For further increase of the strength of interaction, these clusters collapse into a HSS followed by a transition to IHSSs where all the oscillators populate either of the two stable steady states. We analytically determine the origin of HSS and its transition to IHSS in relation to the number of repulsive mean-field links and the strength of interaction using a reductionism approach to the model network. We verify the results with numerical examples of the paradigmatic Landau-Stuart limit cycle system and the chaotic Rössler oscillator as dynamical nodes. During the transition from HSS to IHSSs, the network follows the Turing type symmetry breaking pitchfork or transcritical bifurcation depending upon the system dynamics.

Energy States of Molecules

ERIC Educational Resources Information Center

Hollenberg, J. Leland

1970-01-01

Discusses molecular spectroscopy arising from transitions within rotational, vibrational, and electronic energy states. Using quantum mechanical formuli, the author describes how these spectroscopic methods can be used to determine internuclear distances, bond energies, bond angles, dipole moments, and other details. Concludes with a selected…

Direct mapping of the angle-dependent barrier to reaction for Cl + CHD3 using polarized scattering data

NASA Astrophysics Data System (ADS)

Pan, Huilin; Wang, Fengyan; Czakó, Gábor; Liu, Kopin

2017-12-01

The transition state, which gates and modulates reactive flux, serves as the central concept in our understanding of activated reactions. The barrier height of the transition state can be estimated from the activation energy taken from thermal kinetics data or from the energetic threshold in the measured excitation function (the dependence of reaction cross-sections on initial collision energies). However, another critical and equally important property, the angle-dependent barrier to reaction, has not yet been amenable to experimental determination until now. Here, using the benchmark reaction of Cl + CHD3(v1 = 1) as an example, we show how to map this anisotropic property of the transition state as a function of collision energy from the preferred reactant bond alignment of the backward-scattered products—the imprints of small impact-parameter collisions. The deduced bend potential at the transition state agrees with ab initio calculations. We expect that the method should be applicable to many other direct reactions with a collinear barrier.

DEPRESSIVE SYMPTOMS AND FUNCTIONAL TRANSITIONS OVER TIME IN OLDER PERSONS

PubMed Central

Barry, Lisa C.; Murphy, Terrence E.; Gill, Thomas M.

2010-01-01

Objective We determined the association between clinically significant depressive symptoms, often referred to as depression, and subsequent transitions between no disability, mild disability, severe disability, and death. Design Prospective cohort study. Setting General community in greater New Haven, Connecticut, from March 23, 1998, to December 31, 2008. Participants Seven-hundred fifty four persons, aged 70 years or older. Measurements Monthly assessments of disability in essential activities of daily living and assessments of depressive symptoms every 18 months using a short-form of the Center for Epidemiologic Studies of Depression Scale for up to 129 months. Results Depressed participants were more likely than those who were non-depressed to transition from a state of no disability to mild (HR= 1.52; 95% CI 1.25, 1.85) and severe disability (HR=1.57; 95% CI 1.22, 2.01), and from a state of mild disability to severe disability (HR=1.33; 95% CI 1.06, 1.65); and were less likely to transition from a state of mild disability to no disability (HR=0.69; 95% CI 0.57, 0.85) and from a state of severe disability to no disability (HR=0.50; 95% CI 0.31, 0.79). Conclusions Depressive symptoms are associated with transitions into and out of disabled states, and with increased likelihood of transitioning from mild to severe disability. More broadly, our findings underscore the complexity of the relationship between depressive symptoms and disability. Future work is needed to evaluate the likely reciprocal relationship between depression and functional transitions in older persons. PMID:21873834

Isospin symmetry of Tz =±3/2→±1/2 Gamow-Teller transitions in A=41 nuclei

NASA Astrophysics Data System (ADS)

Fujita, Y.; Shimbara, Y.; Adachi, T.; Berg, G. P.; Brown, B. A.; Fujita, H.; Hatanaka, K.; Kamiya, J.; Nakanishi, K.; Sakemi, Y.; Sasaki, S.; Shimizu, Y.; Tameshige, Y.; Uchida, M.; Wakasa, T.; Yosoi, M.

2004-11-01

Under the assumption that isospin T is a good quantum number, isobaric analog states and various analogous transitions are expected in isobars with mass number A . The strengths of Tz =±3/2→±1/2 analogous Gamow-Teller (GT) transitions and analogous M1 transitions within the A=41 isobar quartet are compared in detail. The Tz =+3/2→+1/2 GT transitions from the Jπ = 3/2+ ground state of 41K leading to excited Jπ = 1/2+ , 3/2+ , and 5/2+ states in 41Ca were measured using the ( 3He ,t) charge-exchange reaction. With a high energy resolution of 35 keV , many fragmented states were observed, and the GT strength distribution was determined up to 10 MeV excitation energy ( Ex ) . The main part of the strength was concentrated in the Ex =4 6 MeV region. A shell-model calculation could reproduce the concentration, but not so well details of the strength distribution. The obtained distribution was further compared with two results of 41Ti β decay studying the analogous Tz =-3/2→-1/2 GT strengths. They reported contradicting distributions. One-to-one correspondences of analogous transitions and analog states were assigned up to Ex =6 MeV in the comparison with one of these 41Ti β -decay results. Combining the spectroscopic information of the analog states in 41Ca and 41Sc , the most probable Jπ values were deduced for each pair of analog states. It was found that 5/2+ states carry the main part of the observed GT strength, while much less GT strength was carried by 1/2+ and 3/2+ states. The gross features of the GT strength distributions for each J were similar for the isospin analogous Tz =±3/2→±1/2 transitions, but the details were somewhat different. From the difference of the distributions, isospin-asymmetry matrix elements of ≈8 keV were deduced. The Coulomb displacement energy, which is sensitive to the configuration of states, showed a sudden increase of about 50 keV at the excitation energy of 3.8 MeV . The strengths of several M1 transitions to the IAS in 41Ca were compared with the strengths of analogous GT transitions. It was found that ratios of the M1 and GT transition strengths were similar, suggesting that the contributions of the ℓτ term in M1 transitions are small.

State transitions and physicochemical aspects of cryoprotection and stabilization in freeze-drying of Lactobacillus rhamnosus GG (LGG).

PubMed

Pehkonen, K S; Roos, Y H; Miao, S; Ross, R P; Stanton, C

2008-06-01

The frozen and dehydrated state transitions of lactose and trehalose were determined and studied as factors affecting the stability of probiotic bacteria to understand physicochemical aspects of protection against freezing and dehydration of probiotic cultures. Lactobacillus rhamnosus GG was frozen (-22 or -43 degrees C), freeze-dried and stored under controlled water vapour pressure (0%, 11%, 23% and 33% relative vapour pressure) conditions. Lactose, trehalose and their mixture (1 : 1) were used as protective media. These systems were confirmed to exhibit relatively similar state transition and water plasticization behaviour in freeze-concentrated and dehydrated states as determined by differential scanning calorimetry. Ice formation and dehydrated materials were studied using cold-stage microscopy and scanning electron microscopy. Trehalose and lactose-trehalose gave the most effective protection of cell viability as observed from colony forming units after freezing, dehydration and storage. Enhanced cell viability was observed when the freezing temperature was -43 degrees C. State transitions of protective media affect ice formation and cell viability in freeze-drying and storage. Formation of a maximally freeze-concentrated matrix with entrapped microbial cells is essential in freezing prior to freeze-drying. Freeze-drying must retain a solid amorphous state of protectant matrices. Freeze-dried matrices contain cells entrapped in the protective matrices in the freezing process. The retention of viability during storage seems to be controlled by water plasticization of the protectant matrix and possibly interactions of water with the dehydrated cells. Highest cell viability was obtained in glassy protective media. This study shows that physicochemical properties of protective media affect the stability of dehydrated cultures. Trehalose and lactose may be used in combination, which is particularly important for the stabilization of probiotic bacteria in dairy systems.

Laser Spectroscopy and AB Initio Calculations on the TaF Molecule

NASA Astrophysics Data System (ADS)

Ng, Kiu Fung; Zou, Wenli; Liu, Wenjian; Cheung, Allan S. C.

2016-06-01

Electronic transition spectrum of the tantalum monoflouride (TaF) molecule in the spectral region between 448 and 520 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Sixteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into six electronic transition systems and the ground state has been identified to be the X3Σ-(0+) state with bond length, ro, and equilibrium vibrational frequency, ωe, determined to be 1.8209 Å and 700.1 wn respectively. In addition, four vibrational bands belong to another transition system involving lower state with Ω = 2 component has also been analyzed. All observed transitions are with ΔΩ = 0. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The Λ-S and Ω states of TaF were calculated at the state-averaged complete active space self-consistent field (SA-CASSCF) and the subsequent internally contracted multi-reference configuration interaction with singles and doubles and Davidson's cluster correction (MRCISD+Q) levels of theory with the active space of 4 electrons in 6 orbitals, that is, the molecular orbitals corresponding to Ta 5d6s are active. The spin-orbit coupling (SOC) is calculated by the state-interaction approach at the SA-CASSCF level via the relativistic effective core potentials (RECPs) spin-orbit operator, where the diagonal elements of the spin-orbit matrix are replaced by the above MRCISD+Q energies. The spectroscopic properties of the ground and many low-lying electronic states of the TaF molecule will be reported. With respect to the observed electronic states in this work, the calculated results are in good agreement with our experimental determinations. This work represents the first experimental investigation of the molecular structure of the TaF molecule.

Capturing the state transitions of seizure-like events using Hidden Markov models.

PubMed

Guirgis, Mirna; Serletis, Demitre; Carlen, Peter L; Bardakjian, Berj L

2011-01-01

The purpose of this study was to investigate the number of states present in the progression of a seizure-like event (SLE). Of particular interest is to determine if there are more than two clearly defined states, as this would suggest that there is a distinct state preceding an SLE. Whole-intact hippocampus from C57/BL mice was used to model epileptiform activity induced by the perfusion of a low Mg(2+)/high K(+) solution while extracellular field potentials were recorded from CA3 pyramidal neurons. Hidden Markov models (HMM) were used to model the state transitions of the recorded SLEs by incorporating various features of the Hilbert transform into the training algorithm; specifically, 2- and 3-state HMMs were explored. Although the 2-state model was able to distinguish between SLE and nonSLE behavior, it provided no improvements compared to visual inspection alone. However, the 3-state model was able to capture two distinct nonSLE states that visual inspection failed to discriminate. Moreover, by developing an HMM based system a priori knowledge of the state transitions was not required making this an ideal platform for seizure prediction algorithms.

Calorimetric Measurements of Magnetic-Field-Induced Inhomogeneous Superconductivity Above the Paramagnetic Limit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agosta, Charles C.; Fortune, Nathanael A.; Hannahs, Scott T.

We report the first magnetocaloric and calorimetric observations of a magnetic-field-induced phase transition within a superconducting state to the long-sought exotic Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) superconducting state, first predicted over 50 years ago. Through the combination of bulk thermodynamic calorimetric and magnetocaloric measurements in the organic superconductor. kappa-(BEDT-TTF)(2) Cu(NCS)(2) as a function of temperature, magnetic field strength, and magnetic field orientation, we establish for the first time that this field-induced first-order phase transition at the paramagnetic limit Hp is a transition to a higher-entropy superconducting phase, uniquely characteristic of the FFLO state. We also establish that this high-field superconducting state displays themore » bulk paramagnetic ordering of spin domains required of the FFLO state. These results rule out the alternate possibility of spin-density wave ordering in the high-field superconducting phase. The phase diagram determined from our measurements-including the observation of a phase transition into the FFLO phase at Hp-is in good agreement with recent NMR results and our own earlier tunnel-diode magnetic penetration depth experiments but is in disagreement with the only previous calorimetric report.« less

Calorimetric Measurements of Magnetic-Field-Induced Inhomogeneous Superconductivity Above the Paramagnetic Limit

NASA Astrophysics Data System (ADS)

Agosta, Charles C.; Fortune, Nathanael A.; Hannahs, Scott T.; Gu, Shuyao; Liang, Lucy; Park, Ju-Hyun; Schleuter, John A.

2017-06-01

We report the first magnetocaloric and calorimetric observations of a magnetic-field-induced phase transition within a superconducting state to the long-sought exotic Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) superconducting state, first predicted over 50 years ago. Through the combination of bulk thermodynamic calorimetric and magnetocaloric measurements in the organic superconductor κ -(BEDT -TTF )2Cu (NCS )2 as a function of temperature, magnetic field strength, and magnetic field orientation, we establish for the first time that this field-induced first-order phase transition at the paramagnetic limit Hp is a transition to a higher-entropy superconducting phase, uniquely characteristic of the FFLO state. We also establish that this high-field superconducting state displays the bulk paramagnetic ordering of spin domains required of the FFLO state. These results rule out the alternate possibility of spin-density wave ordering in the high-field superconducting phase. The phase diagram determined from our measurements—including the observation of a phase transition into the FFLO phase at Hp—is in good agreement with recent NMR results and our own earlier tunnel-diode magnetic penetration depth experiments but is in disagreement with the only previous calorimetric report.

Einstein A coefficients for rovibronic lines of the A2Π → X2Σ+ and B2Σ+ → X2Σ+ transitions of CaH and CaD

NASA Astrophysics Data System (ADS)

Alavi, S. Fatemeh; Shayesteh, Alireza

2018-02-01

Calcium monohydride is an important diatomic molecule appearing in the spectra of sunspots and M dwarfs. We report complete line lists with Einstein A coefficients for the A2Π-X2Σ+ and B2Σ+-X2Σ+ electronic transitions of CaH and CaD radicals. The most recent ab initio transition dipole moments and potential energy curves were used for the calculation of vibronic band intensities, taking the Herman-Wallis effect into account, and the rotational line strengths were calculated using the PGOPHER program of Western. For the A2Π and B2Σ+ excited states of CaH and CaD, new off-diagonal electronic matrix elements were included in the Hamiltonian matrix, and new sets of spectroscopic constants were determined in order to accurately reproduce the line positions and relative intensities of the observed branches in laboratory spectra. For both CaH and CaD isotopologues, Einstein A coefficients were calculated for all possible rovibronic transitions from the v΄ = 0-3 vibrational levels of the A2Π state and the v΄ = 0-2 vibrational levels of the B2Σ+ state to the v″ = 0-4 vibrational levels of the X2Σ+ ground state. The line lists and intensities reported here can be used to accurately determine the amounts of CaH and CaD in stellar environments.

Directional properties in photodissociation: a probe for the symmetry and geometry of excited states of dimethylnitrosamine and tert-butyl nitrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lavi, R.; Schwartz-Lavi, I.B.; Rosenwaks, S.

1987-10-08

The rotational alignment, ..lambda..-doubling, and spin-orbit populations of the NO fragment following the photodissociation of (CH/sub 3/)/sub 2/NNO and (CH/sub 3/)/sub 3/CONO in different absorption bands are determined. The results for the S/sub 1/(n..pi..*) withdraws S/sub 0/ and S/sub 2/(..pi pi..*) withdraws S/sub 0/ transitions in both molecules indicate planarity of the fragmentation processes and an A'' symmetry of the S/sub 1/ state. For the S/sub 2/(..pi pi..*) withdraws S/sub 0/ transition in (CH/sub 3/)/sub 2/NNO the results imply an A' symmetry of the S/sub 2/ state. The values obtained for the alignment are indicative of the difference between themore » directions of the transition dipole moment for the S/sub 1/(n..pi..*) withdraws S/sub 0/ and the S/sub 2/(..pi pi..*) withdraws S/sub 0/ transitions.« less

A Molecular Iodine Spectral Data Set for Rovibronic Analysis

ERIC Educational Resources Information Center

Williamson, J. Charles; Kuntzleman, Thomas S.; Kafader, Rachael A.

2013-01-01

A data set of 7,381 molecular iodine vapor rovibronic transitions between the X and B electronic states has been prepared for an advanced undergraduate spectroscopic analysis project. Students apply standard theoretical techniques to these data and determine the values of three X-state constants (image omitted) and four B-state constants (image…

Lifetime measurements of high-lying short lived states in {sup 69}As

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matejska-Minda, M.; Bednarczyk, P.; Fornal, B.

2012-10-20

Lifetimes of high-spin states in {sup 69}As have been measured using Doppler shift attenuation technique with the GASP and RFD setup. The determined transition probabilities indicate large deformation associated with some rotational bands in this nucleus.

Artificial emotion triggered stochastic behavior transitions with motivational gain effects for multi-objective robot tasks

NASA Astrophysics Data System (ADS)

Dağlarli, Evren; Temeltaş, Hakan

2007-04-01

This paper presents artificial emotional system based autonomous robot control architecture. Hidden Markov model developed as mathematical background for stochastic emotional and behavior transitions. Motivation module of architecture considered as behavioral gain effect generator for achieving multi-objective robot tasks. According to emotional and behavioral state transition probabilities, artificial emotions determine sequences of behaviors. Also motivational gain effects of proposed architecture can be observed on the executing behaviors during simulation.

N(+)-N and O(+)-O interaction energies, dipole transition moments, and transport cross sections

NASA Technical Reports Server (NTRS)

Partridge, H.; Stallcop, J. R.

1986-01-01

Complete sets of ion-atom interaction energies have been computed for nitrogen and oxygen with accurate large scale structure calculations. The computed energies agree well with the accurate potential curves available from spectroscopic measurement. The state functions from the nitrogen calculations have been applied to determine the transition moment for all allowed dipole transitions. These results can be combined to compute a detailed radiation spectrum such as that required to define the highly nonequilibrium environment of aeroassisted orbital transfer vehicle (AOTV). The long-range interaction energies have been used to determine the ion-atom resonance charge exchange cross sections that are important for transport processes such as diffusion. A calculation to determine reliable transport properties for energies that include the AOTV temperature range from these computed properties is described.

Diagnostic transitions in mild cognitive impairment subtypes.

PubMed

Forlenza, Orestes Vicente; Diniz, Breno Satler; Nunes, Paula Villela; Memória, Claudia Maia; Yassuda, Monica Sanches; Gattaz, Wagner Farid

2009-12-01

At least for a subset of patients, the clinical diagnosis of mild cognitive impairment (MCI) may represent an intermediate stage between normal aging and dementia. Nevertheless, the patterns of transition of cognitive states between normal cognitive aging and MCI to dementia are not well established. In this study we address the pattern of transitions between cognitive states in patients with MCI and healthy controls, prior to the conversion to dementia. 139 subjects (78% women, mean age, 68.5 +/- 6.1 years; mean educational level, 11.7 +/- 5.4 years) were consecutively assessed in a memory clinic with a standardized clinical and neuropsychological protocol, and classified as cognitively healthy (normal controls) or with MCI (including subtypes) at baseline. These subjects underwent annual reassessments (mean duration of follow-up: 2.7 +/- 1.1 years), in which cognitive state was ascertained independently of prior diagnoses. The pattern of transitions of the cognitive state was determined by Markov chain analysis. The transitions from one cognitive state to another varied substantially between MCI subtypes. Single-domain MCI (amnestic and non-amnestic) more frequently returned to normal cognitive state upon follow-up (22.5% and 21%, respectively). Among subjects who progressed to Alzheimer's disease (AD), the most common diagnosis immediately prior conversion was multiple-domain MCI (85%). The clinical diagnosis of MCI and its subtypes yields groups of patients with heterogeneous patterns of transitions between one given cognitive state to another. The presence of more severe and widespread cognitive deficits, as indicated by the group of multiple-domain amnestic MCI may be a better predictor of AD than single-domain amnestic or non-amnestic deficits. These higher-risk individuals could probably be the best candidates for the development of preventive strategies and early treatment for the disease.

Topological phase transition and evolution of edge states in In-rich InGaN/GaN quantum wells under hydrostatic pressure

NASA Astrophysics Data System (ADS)

Łepkowski, S. P.; Bardyszewski, W.

2017-02-01

Combining the k · p method with the third-order elasticity theory, we perform a theoretical study of the pressure-induced topological phase transition and the pressure evolution of topologically protected edge states in InN/GaN and In-rich InGaN/GaN quantum wells. We show that for a certain range of the quantum well parameters, thanks to a negative band gap pressure coefficient, it is possible to continuously drive the system from the normal insulator state through the topological insulator into the semimetal phase. The critical pressure for the topological phase transition depends not only on the quantum well thickness but also on the width of the Hall bar, which determines the coupling between the edge states localized at the opposite edges. We also find that in narrow Hall bar structures, near the topological phase transition, a significant Rashba-type spin splitting of the lower and upper branches of the edge state dispersion curve appears. This effect originates from the lack of the mirror symmetry of the quantum well potential caused by the built-in electric field, and can be suppressed by increasing the Hall bar width. When the pressure increases, the energy dispersion of the edge states becomes more parabolic-like and the spin splitting decreases. A further increase of pressure leads to the transition to a semimetal phase, which occurs due to the closure of the indirect 2D bulk band gap. The difference between the critical pressure at which the system becomes semimetallic, and the pressure for the topological phase transition, correlates with the variation of the pressure coefficient of the band gap in the normal insulator state.

Topological phase transition and evolution of edge states in In-rich InGaN/GaN quantum wells under hydrostatic pressure.

PubMed

Łepkowski, S P; Bardyszewski, W

2017-02-08

Combining the k · p method with the third-order elasticity theory, we perform a theoretical study of the pressure-induced topological phase transition and the pressure evolution of topologically protected edge states in InN/GaN and In-rich InGaN/GaN quantum wells. We show that for a certain range of the quantum well parameters, thanks to a negative band gap pressure coefficient, it is possible to continuously drive the system from the normal insulator state through the topological insulator into the semimetal phase. The critical pressure for the topological phase transition depends not only on the quantum well thickness but also on the width of the Hall bar, which determines the coupling between the edge states localized at the opposite edges. We also find that in narrow Hall bar structures, near the topological phase transition, a significant Rashba-type spin splitting of the lower and upper branches of the edge state dispersion curve appears. This effect originates from the lack of the mirror symmetry of the quantum well potential caused by the built-in electric field, and can be suppressed by increasing the Hall bar width. When the pressure increases, the energy dispersion of the edge states becomes more parabolic-like and the spin splitting decreases. A further increase of pressure leads to the transition to a semimetal phase, which occurs due to the closure of the indirect 2D bulk band gap. The difference between the critical pressure at which the system becomes semimetallic, and the pressure for the topological phase transition, correlates with the variation of the pressure coefficient of the band gap in the normal insulator state.

Different secondary structure elements as scaffolds for protein folding transition states of two homologous four-helix bundles.

PubMed

Teilum, Kaare; Thormann, Thorsten; Caterer, Nigel R; Poulsen, Heidi I; Jensen, Peter H; Knudsen, Jens; Kragelund, Birthe B; Poulsen, Flemming M

2005-04-01

Comparison of the folding processes for homologue proteins can provide valuable information about details in the interactions leading to the formation of the folding transition state. Here the folding kinetics of 18 variants of yACBP and 3 variants of bACBP have been studied by Phi-value analysis. In combination with Phi-values from previous work, detailed insight into the transition states for folding of both yACBP and bACBP has been obtained. Of the 16 sequence positions that have been studied in both yACBP and bACBP, 5 (V12, I/L27, Y73, V77, and L80) have high Phi-values and appear to be important for the transition state formation in both homologues. Y31, A34, and A69 have high Phi-values only in yACBP, while F5, A9, and I74 have high Phi-values only in bACBP. Thus, additional interactions between helices A2 and A4 appear to be important for the transition state of yACBP, whereas additional interactions between helices A1 and A4 appear to be important for the transition state of bACBP. To examine whether these differences could be assigned to different packing of the residues in the native state, a solution structure of yACBP was determined by NMR. Small changes in the packing of the hydrophobic side-chains, which strengthen the interactions between helices A2 and A4, are observed in yACBP relative to bACBP. It is suggested that different structure elements serve as scaffolds for the folding of the 2 ACBP homologues. (c) 2005 Wiley-Liss, Inc.

Using fluorescence correlation spectroscopy to study conformational changes in denatured proteins.

PubMed

Sherman, Eilon; Itkin, Anna; Kuttner, Yosef Yehuda; Rhoades, Elizabeth; Amir, Dan; Haas, Elisha; Haran, Gilad

2008-06-01

Fluorescence correlation spectroscopy (FCS) is a sensitive analytical tool that allows dynamics and hydrodynamics of biomolecules to be studied under a broad range of experimental conditions. One application of FCS of current interest is the determination of the size of protein molecules in the various states they sample along their folding reaction coordinate, which can be accessed through the measurement of diffusion coefficients. It has been pointed out that the analysis of FCS curves is prone to artifacts that may lead to erroneous size determination. To set the stage for FCS studies of unfolded proteins, we first show that the diffusion coefficients of small molecules as well as proteins can be determined accurately even in the presence of high concentrations of co-solutes that change the solution refractive index significantly. Indeed, it is found that the Stokes-Einstein relation between the measured diffusion coefficient and solution viscosity holds even in highly concentrated glycerol or guanidinium hydrochloride (GuHCl) solutions. These measurements form the basis for an investigation of the structure of the denatured state of two proteins, the small protein L and the larger, three-domain protein adenylate kinase (AK). FCS is found useful for probing expansion in the denatured state beyond the unfolding transition. It is shown that the denatured state of protein L expands as the denaturant concentration increases, in a process akin to the transition from a globule to a coil in polymers. This process continues at least up to 5 M GuHCl. On the other hand, the denatured state of AK does not seem to expand much beyond 2 M GuHCl, a result that is in qualitative accord with single-molecule fluorescence histograms. Because both the unfolding transition and the coil-globule transition of AK occur at a much lower denaturant concentration than those of protein L, a possible correlation between the two phenomena is suggested.

Lack of multiplicative transitivity in person trade-off responses.

PubMed

Schwarzinger, Michaël; Lanoë, Jean-Louis; Nord, Erik; Durand-Zaleski, Isabelle

2004-02-01

The person trade-off (PTO) is a technique for eliciting preferences for resource allocation across patient groups. In principle PTO responses should satisfy a requirement of multiplicative transitivity, i.e. that if people consider treatment of 1 in state A to be equivalent to treating 10 in state B, and 1 in state B to be equivalent to 10 in state C, then they should find 1 in state A equivalent to 100 in state C. Earlier studies addressing labelled diseases (specific diagnoses), have shown multiplicative intransitivity of the PTO responses. Our purpose was to test multiplicative transitivity in the case of health states described with the EuroQol instrument only and to find a possible framing effect such as the number of persons in the reference intervention. Forty-four master degree students were asked to fill in a questionnaire addressing four chronic health states. Their task consisted in (1). ranking the states by severity, (2). valuing each of them by the means of the time trade-off, and (3). doing the PTO for all the 10 possible pairwise combinations of the four chronic states plus a fatal one. In a subsequent questionnaire the number of persons in the reference intervention in the PTO was increased from 10 to 100. Multiplicative transitivity was studied in subjects who demonstrated a willingness to trade off and consistency in ranking individual values. None of the 39 subjects included satisfied a minimum multiplicative transitivity requirement in PTO responses. Internal consistency was not improved when the PTO involved health states close to each other in terms of severity, nor when the prevention of death was not the reference intervention. For the 22 subjects having answered both types of questionnaire, increasing the number of persons in the reference intervention did not improve multiplicative transitivity. The PTO holds promise as a useful method for determining social preferences for priority setting, inasmuch as it captures distributive concerns that individual utility techniques such as the time trade-off do not address. But the lack of multiplicative transitivity in PTO responses is unsatisfactory, and ways to reduce this problem need to be explored. Copyright 2003 John Wiley & Sons, Ltd.

A Comparison of Transition Predictors between Students Following Different Diploma Pathways

ERIC Educational Resources Information Center

Vierno, Peter Joseph

2013-01-01

The purpose of this study was to determine the extent to which evidence of two secondary transition predictors, paid employment and independent living, exist in the Individualized Education Plans (IEPs) of students on two pathways to a high school diploma in a southeastern state. The IEPs of 538 students were examined from one urban district in…

Deterministic switching of hierarchy during wrinkling in quasi-planar bilayers

DOE PAGES

Saha, Sourabh K.; Culpepper, Martin L.

2016-04-25

Emergence of hierarchy during compression of quasi-planar bilayers is preceded by a mode-locked state during which the quasi-planar form persists. Transition to hierarchy is determined entirely by geometrically observable parameters. This results in a universal transition phase diagram that enables one to deterministically tune hierarchy even with limited knowledge about material properties.

Estimating state-transition probabilities for unobservable states using capture-recapture/resighting data

USGS Publications Warehouse

Kendall, W.L.; Nichols, J.D.

2002-01-01

Temporary emigration was identified some time ago as causing potential problems in capture-recapture studies, and in the last five years approaches have been developed for dealing with special cases of this general problem. Temporary emigration can be viewed more generally as involving transitions to and from an unobservable state, and frequently the state itself is one of biological interest (e.g., 'nonbreeder'). Development of models that permit estimation of relevant parameters in the presence of an unobservable state requires either extra information (e.g., as supplied by Pollock's robust design) or the following classes of model constraints: reducing the order of Markovian transition probabilities, imposing a degree of determinism on transition probabilities, removing state specificity of survival probabilities, and imposing temporal constancy of parameters. The objective of the work described in this paper is to investigate estimability of model parameters under a variety of models that include an unobservable state. Beginning with a very general model and no extra information, we used numerical methods to systematically investigate the use of ancillary information and constraints to yield models that are useful for estimation. The result is a catalog of models for which estimation is possible. An example analysis of sea turtle capture-recapture data under two different models showed similar point estimates but increased precision for the model that incorporated ancillary data (the robust design) when compared to the model with deterministic transitions only. This comparison and the results of our numerical investigation of model structures lead to design suggestions for capture-recapture studies in the presence of an unobservable state.

Determination of differential cross sections for electron-impact excitation of electronic states of molecular oxygen

NASA Astrophysics Data System (ADS)

Campbell, L.; Green, M. A.; Brunger, M. J.; Teubner, P. J.; Cartwright, D. C.

2000-02-01

The development and initial results of a method for the determination of differential cross sections for electron scattering by molecular oxygen are described. The method has been incorporated into an existing package of computer programs which, given spectroscopic factors, dissociation energies and an energy-loss spectrum for electron-impact excitation, determine the differential cross sections for each electronic state relative to that of the elastic peak. Enhancements of the original code were made to deal with particular aspects of electron scattering from O2, such as the overlap of vibrational levels of the ground state with transitions to excited states, and transitions to levels close to and above the dissocation energy in the Herzberg and Schumann-Runge continua. The utility of the code is specifically demonstrated for the ``6-eV states'' of O2, where we report absolute differential cross sections for their excitation by 15-eV electrons. In addition an integral cross section, derived from the differential cross section measurements, is also reported for this excitation process and compared against available theoretical results. The present differential and integral cross sections for excitation of the ``6-eV states'' of O2 are the first to be reported in the literature for electron-impact energies below 20 eV.

Accurate determination of the fine-structure intervals in the 3P ground states of C-13 and C-12 by far-infrared laser magnetic resonance

NASA Technical Reports Server (NTRS)

Cooksy, A. L.; Saykally, R. J.; Brown, J. M.; Evenson, K. M.

1986-01-01

Accurate values are presented for the fine-structure intervals in the 3P ground state of neutral atomic C-12 and C-13 as obtained from laser magnetic resonance spectroscopy. The rigorous analysis of C-13 hyperfine structure, the measurement of resonant fields for C-12 transitions at several additional far-infrared laser frequencies, and the increased precision of the C-12 measurements, permit significant improvement in the evaluation of these energies relative to earlier work. These results will expedite the direct and precise measurement of these transitions in interstellar sources and should assist in the determination of the interstellar C-12/C-13 abundance ratio.

Inelastic collision processes in ozone and their relation to atmospheric pressure broadening

NASA Technical Reports Server (NTRS)

Steinfeld, J. I.; Flannery, C.; Klaassen, J.; Mizugai, Y.; Spencer, M.

1990-01-01

The research task employs infrared double-resonance to determine rotational energy transfer rates and pathways, in both the ground and vibrationally excited states of ozone. The resulting data base will then be employed to test inelastic scattering theories and to assess intermolecular potential models, both of which are necessary for the systematization and prediction of infrared pressure-broadening coefficients, which are in turn required by atmospheric ozone monitoring techniques based on infrared remote sensing. In addition, observation of excited-state absorption transitions will permit us to improve the determination of the 2 nu(sub 3), nu(sub 1) + nu(sub 2), and 2 nu(sub 1) rotational constants and to derive band strengths for hot-band transitions involving these levels.

Characterization of the hyperfine interaction of the excited D50 state of Eu3 +:Y2SiO5

NASA Astrophysics Data System (ADS)

Cruzeiro, Emmanuel Zambrini; Etesse, Jean; Tiranov, Alexey; Bourdel, Pierre-Antoine; Fröwis, Florian; Goldner, Philippe; Gisin, Nicolas; Afzelius, Mikael

2018-03-01

We characterize the europium (Eu3 +) hyperfine interaction of the excited state (D50) and determine its effective spin Hamiltonian parameters for the Zeeman and quadrupole tensors. An optical free induction decay method is used to measure all hyperfine splittings under a weak external magnetic field (up to 10 mT) for various field orientations. On the basis of the determined Hamiltonian, we discuss the possibility to predict optical transition probabilities between hyperfine levels for the F70⟷D50 transition. The obtained results provide necessary information to realize an optical quantum memory scheme which utilizes long spin coherence properties of 3 + 151Eu :Y2SiO5 material under external magnetic fields.

Experimental Energy Levels and Partition Function of the 12C2 Molecule

NASA Astrophysics Data System (ADS)

Furtenbacher, Tibor; Szabó, István; Császár, Attila G.; Bernath, Peter F.; Yurchenko, Sergei N.; Tennyson, Jonathan

2016-06-01

The carbon dimer, the 12C2 molecule, is ubiquitous in astronomical environments. Experimental-quality rovibronic energy levels are reported for 12C2, based on rovibronic transitions measured for and among its singlet, triplet, and quintet electronic states, reported in 42 publications. The determination utilizes the Measured Active Rotational-Vibrational Energy Levels (MARVEL) technique. The 23,343 transitions measured experimentally and validated within this study determine 5699 rovibronic energy levels, 1325, 4309, and 65 levels for the singlet, triplet, and quintet states investigated, respectively. The MARVEL analysis provides rovibronic energies for six singlet, six triplet, and two quintet electronic states. For example, the lowest measurable energy level of the {{a}}{}3{{{\\Pi }}}{{u}} state, corresponding to the J = 2 total angular momentum quantum number and the F 1 spin-multiplet component, is 603.817(5) cm-1. This well-determined energy difference should facilitate observations of singlet-triplet intercombination lines, which are thought to occur in the interstellar medium and comets. The large number of highly accurate and clearly labeled transitions that can be derived by combining MARVEL energy levels with computed temperature-dependent intensities should help a number of astrophysical observations as well as corresponding laboratory measurements. The experimental rovibronic energy levels, augmented, where needed, with ab initio variational ones based on empirically adjusted and spin-orbit coupled potential energy curves obtained using the Duo code, are used to obtain a highly accurate partition function, and related thermodynamic data, for 12C2 up to 4000 K.

Fostering Health: The Affordable Care Act, Medicaid, and Youth Transitioning from Foster Care. Policy Brief

ERIC Educational Resources Information Center

Wilson-Simmons, Renée; Dworsky, Amy; Tongue, Denzel; Hulbutta, Marikate

2016-01-01

The Affordable Care Act includes language that requires states to provide Medicaid coverage to youth who were in foster care in their state before aging out of the child welfare system. However, most states have interpreted the law differently for youth who move to their state after aging out, determining that automatic Medicaid coverage is an…

Identification of significant E0 strength in the 22+ → 21+ transitions of 58,60,62Ni

NASA Astrophysics Data System (ADS)

Evitts, L. J.; Garnsworthy, A. B.; Kibédi, T.; Smallcombe, J.; Reed, M. W.; Brown, B. A.; Stuchbery, A. E.; Lane, G. J.; Eriksen, T. K.; Akber, A.; Alshahrani, B.; de Vries, M.; Gerathy, M. S. M.; Holt, J. D.; Lee, B. Q.; McCormick, B. P.; Mitchell, A. J.; Moukaddam, M.; Mukhopadhyay, S.; Palalani, N.; Palazzo, T.; Peters, E. E.; Ramirez, A. P. D.; Stroberg, S. R.; Tornyi, T.; Yates, S. W.

2018-04-01

The E0 transition strength in the 22+ →21 + transitions of 58,60,62Ni have been determined for the first time following a series of measurements at the Australian National University (ANU) and the University of Kentucky (UK). The CAESAR Compton-suppressed HPGe array and the Super-e solenoid at ANU were used to measure the δ (E 2 / M 1) mixing ratio and internal conversion coefficient of each transition following inelastic proton scattering. Level half-lives, δ (E 2 / M 1) mixing ratios and γ-ray branching ratios were measured at UK following inelastic neutron scattering. The new spectroscopic information was used to determine the E0 strengths. These are the first 2+ →2+E0 transition strengths measured in nuclei with spherical ground states and the E0 component is found to be unexpectedly large; in fact, these are amongst the largest E0 transition strengths in medium and heavy nuclei reported to date.

Spin injection and spin transport in paramagnetic insulators

DOE PAGES

Okamoto, Satoshi

2016-02-22

We investigate the spin injection and the spin transport in paramagnetic insulators described by simple Heisenberg interactions using auxiliary particle methods. Some of these methods allow access to both paramagnetic states above magnetic transition temperatures and magnetic states at low temperatures. It is predicted that the spin injection at an interface with a normal metal is rather insensitive to temperatures above the magnetic transition temperature. On the other hand below the transition temperature, it decreases monotonically and disappears at zero temperature. We also analyze the bulk spin conductance. We show that the conductance becomes zero at zero temperature as predictedmore » by linear spin wave theory but increases with temperature and is maximized around the magnetic transition temperature. These findings suggest that the compromise between the two effects determines the optimal temperature for spintronics applications utilizing magnetic insulators.« less

Collisional excitation of molecules in dense interstellar clouds

NASA Technical Reports Server (NTRS)

Green, S.

1985-01-01

State transitions which permit the identification of the molecular species in dense interstellar clouds are reviewed, along with the techniques used to calculate the transition energies, the database on known molecular transitions and the accuracy of the values. The transition energies cannot be measured directly and therefore must be modeled analytically. Scattering theory is used to determine the intermolecular forces on the basis of quantum mechanics. The nuclear motions can also be modeled with classical mechanics. Sample rate constants are provided for molecular systems known to inhabit dense interstellar clouds. The values serve as a database for interpreting microwave and RF astrophysical data on the transitions undergone by interstellar molecules.

Demodulator for binary-phase modulated signals having a variable clock rate

NASA Technical Reports Server (NTRS)

Wu, Ta Tzu (Inventor)

1976-01-01

Method and apparatus for demodulating binary-phase modulated signals recorded on a magnetic stripe on a card as the card is manually inserted into a card reader. Magnetic transitions are sensed as the card is read and the time interval between immediately preceeding basic transitions determines the duration of a data sampling pulse which detects the presence or absence of an intermediate transition pulse indicative of two respective logic states. The duration of the data sampling pulse is approximately 75 percent of the preceeding interval between basic transitions to permit tracking succeeding time differences in basic transition intervals of up to approximately 25 percent.

Exploring the origins of topological frustration: Design of a minimally frustrated model of fragment B of protein A

PubMed Central

Shea, Joan-Emma; Onuchic, José N.; Brooks, Charles L.

1999-01-01

Topological frustration in an energetically unfrustrated off-lattice model of the helical protein fragment B of protein A from Staphylococcus aureus was investigated. This Gō-type model exhibited thermodynamic and kinetic signatures of a well-designed two-state folder with concurrent collapse and folding transitions and single exponential kinetics at the transition temperature. Topological frustration is determined in the absence of energetic frustration by the distribution of Fersht φ values. Topologically unfrustrated systems present a unimodal distribution sharply peaked at intermediate φ, whereas highly frustrated systems display a bimodal distribution peaked at low and high φ values. The distribution of φ values in protein A was determined both thermodynamically and kinetically. Both methods yielded a unimodal distribution centered at φ = 0.3 with tails extending to low and high φ values, indicating the presence of a small amount of topological frustration. The contacts with high φ values were located in the turn regions between helices I and II and II and III, intimating that these hairpins are in large part required in the transition state. Our results are in good agreement with all-atom simulations of protein A, as well as lattice simulations of a three- letter code 27-mer (which can be compared with a 60-residue helical protein). The relatively broad unimodal distribution of φ values obtained from the all-atom simulations and that from the minimalist model for the same native fold suggest that the structure of the transition state ensemble is determined mostly by the protein topology and not energetic frustration. PMID:10535953

A reduced-amide inhibitor of Pin1 binds in a conformation resembling a twisted-amide transition state.

PubMed

Xu, Guoyan G; Zhang, Yan; Mercedes-Camacho, Ana Y; Etzkorn, Felicia A

2011-11-08

The mechanism of the cell cycle regulatory peptidyl prolyl isomerase (PPIase), Pin1, was investigated using reduced-amide inhibitors designed to mimic the twisted-amide transition state. Inhibitors, R-pSer-Ψ[CH(2)N]-Pro-2-(indol-3-yl)ethylamine, 1 [R = fluorenylmethoxycarbonyl (Fmoc)] and 2 (R = Ac), of Pin1 were synthesized and bioassayed. Inhibitor 1 had an IC(50) value of 6.3 μM, which is 4.5-fold better for Pin1 than our comparable ground-state analogue, a cis-amide alkene isostere-containing inhibitor. The change of Fmoc to Ac in 2 improved aqueous solubility for structural determination and resulted in an IC(50) value of 12 μM. The X-ray structure of the complex of 2 bound to Pin1 was determined to 1.76 Å resolution. The structure revealed that the reduced amide adopted a conformation similar to the proposed twisted-amide transition state of Pin1, with a trans-pyrrolidine conformation of the prolyl ring. A similar conformation of substrate would be destabilized relative to the planar amide conformation. Three additional reduced amides, with Thr replacing Ser and l- or d-pipecolate (Pip) replacing Pro, were slightly weaker inhibitors of Pin1.

Transition probabilities in neutron-rich Se,8684

NASA Astrophysics Data System (ADS)

Litzinger, J.; Blazhev, A.; Dewald, A.; Didierjean, F.; Duchêne, G.; Fransen, C.; Lozeva, R.; Sieja, K.; Verney, D.; de Angelis, G.; Bazzacco, D.; Birkenbach, B.; Bottoni, S.; Bracco, A.; Braunroth, T.; Cederwall, B.; Corradi, L.; Crespi, F. C. L.; Désesquelles, P.; Eberth, J.; Ellinger, E.; Farnea, E.; Fioretto, E.; Gernhäuser, R.; Goasduff, A.; Görgen, A.; Gottardo, A.; Grebosz, J.; Hackstein, M.; Hess, H.; Ibrahim, F.; Jolie, J.; Jungclaus, A.; Kolos, K.; Korten, W.; Leoni, S.; Lunardi, S.; Maj, A.; Menegazzo, R.; Mengoni, D.; Michelagnoli, C.; Mijatovic, T.; Million, B.; Möller, O.; Modamio, V.; Montagnoli, G.; Montanari, D.; Morales, A. I.; Napoli, D. R.; Niikura, M.; Pollarolo, G.; Pullia, A.; Quintana, B.; Recchia, F.; Reiter, P.; Rosso, D.; Sahin, E.; Salsac, M. D.; Scarlassara, F.; Söderström, P.-A.; Stefanini, A. M.; Stezowski, O.; Szilner, S.; Theisen, Ch.; Valiente Dobón, J. J.; Vandone, V.; Vogt, A.

2015-12-01

Reduced quadrupole transition probabilities for low-lying transitions in neutron-rich Se,8684 are investigated with a recoil distance Doppler shift (RDDS) experiment. The experiment was performed at the Istituto Nazionale di Fisica Nucleare (INFN) Laboratori Nazionali di Legnaro using the Cologne Plunger device for the RDDS technique and the AGATA Demonstrator array for the γ -ray detection coupled to the PRISMA magnetic spectrometer for an event-by-event particle identification. In 86Se the level lifetime of the yrast 21+ state and an upper limit for the lifetime of the 41+ state are determined for the first time. The results of 86Se are in agreement with previously reported predictions of large-scale shell-model calculations using Ni78-I and Ni78-II effective interactions. In addition, intrinsic shape parameters of lowest yrast states in 86Se are calculated. In semimagic 84Se level lifetimes of the yrast 41+ and 61+ states are determined for the first time. Large-scale shell-model calculations using effective interactions Ni78-II, JUN45, jj4b, and jj4pna are performed. The calculations describe B (E 2 ;21+→01+) and B (E 2 ;61+→41+) fairly well and point out problems in reproducing the experimental B (E 2 ;41+→21+) .

Millimeter-wave spectroscopy of syn formyl azide (HC(O)N3) in seven vibrational states

NASA Astrophysics Data System (ADS)

Walters, Nicholas A.; Amberger, Brent K.; Esselman, Brian J.; Woods, R. Claude; McMahon, Robert J.

2017-01-01

Millimeter-wave spectra for formyl azide (HC(O)N3) were obtained from 240 to 360 GHz at ambient temperature. For the ground state of syn formyl azide, over 1500 independent rotational transitions were measured and least-squares fit to a complete S-reduced 8th order centrifugal distortion/rigid rotor Hamiltonian. The decomposition of formyl azide was monitored over a period of several hours, the half-life (t½ = 30 min) was determined, and its decomposition products were investigated. Transitions from five vibrational satellites of syn formyl azide (ν9, ν12, 2ν9, ν9 + ν12, and ν11) were observed, measured, and least-squares fit to complete or nearly complete octic centrifugally-distorted, single-state S-reduced models. A less complete single-state fit of 3ν9 (509.3 cm-1) was obtained from an unperturbed subset of its assignable transitions. This state is apparently coupled to the fundamental ν8 (489.4 cm-1) and the overtone 2ν12 (503.6 cm-1), but the coupling remains unanalyzed. Anharmonic CCSD(T)/ANO1 estimates of the vibrational frequencies of syn formyl azide were in close agreement with previously published experimental and computational values. Experimentally determined vibration-rotation interaction (αi) values were in excellent agreement with coupled-cluster predicted αi values for the fundamentals ν9, ν12, and ν11.

Coupled Flip-Flop Model for REM Sleep Regulation in the Rat

PubMed Central

Dunmyre, Justin R.; Mashour, George A.; Booth, Victoria

2014-01-01

Recent experimental studies investigating the neuronal regulation of rapid eye movement (REM) sleep have identified mutually inhibitory synaptic projections among REM sleep-promoting (REM-on) and REM sleep-inhibiting (REM-off) neuronal populations that act to maintain the REM sleep state and control its onset and offset. The control mechanism of mutually inhibitory synaptic interactions mirrors the proposed flip-flop switch for sleep-wake regulation consisting of mutually inhibitory synaptic projections between wake- and sleep-promoting neuronal populations. While a number of synaptic projections have been identified between these REM-on/REM-off populations and wake/sleep-promoting populations, the specific interactions that govern behavioral state transitions have not been completely determined. Using a minimal mathematical model, we investigated behavioral state transition dynamics dictated by a system of coupled flip-flops, one to control transitions between wake and sleep states, and another to control transitions into and out of REM sleep. The model describes the neurotransmitter-mediated inhibitory interactions between a wake- and sleep-promoting population, and between a REM-on and REM-off population. We proposed interactions between the wake/sleep and REM-on/REM-off flip-flops to replicate the behavioral state statistics and probabilities of behavioral state transitions measured from experimental recordings of rat sleep under ad libitum conditions and after 24 h of REM sleep deprivation. Reliable transitions from REM sleep to wake, as dictated by the data, indicated the necessity of an excitatory projection from the REM-on population to the wake-promoting population. To replicate the increase in REM-wake-REM transitions observed after 24 h REM sleep deprivation required that this excitatory projection promote transient activation of the wake-promoting population. Obtaining the reliable wake-nonREM sleep transitions observed in the data required that activity of the wake-promoting population modulated the interaction between the REM-on and REM-off populations. This analysis suggests neuronal processes to be targeted in further experimental studies of the regulatory mechanisms of REM sleep. PMID:24722577

Coupled flip-flop model for REM sleep regulation in the rat.

PubMed

Dunmyre, Justin R; Mashour, George A; Booth, Victoria

2014-01-01

Recent experimental studies investigating the neuronal regulation of rapid eye movement (REM) sleep have identified mutually inhibitory synaptic projections among REM sleep-promoting (REM-on) and REM sleep-inhibiting (REM-off) neuronal populations that act to maintain the REM sleep state and control its onset and offset. The control mechanism of mutually inhibitory synaptic interactions mirrors the proposed flip-flop switch for sleep-wake regulation consisting of mutually inhibitory synaptic projections between wake- and sleep-promoting neuronal populations. While a number of synaptic projections have been identified between these REM-on/REM-off populations and wake/sleep-promoting populations, the specific interactions that govern behavioral state transitions have not been completely determined. Using a minimal mathematical model, we investigated behavioral state transition dynamics dictated by a system of coupled flip-flops, one to control transitions between wake and sleep states, and another to control transitions into and out of REM sleep. The model describes the neurotransmitter-mediated inhibitory interactions between a wake- and sleep-promoting population, and between a REM-on and REM-off population. We proposed interactions between the wake/sleep and REM-on/REM-off flip-flops to replicate the behavioral state statistics and probabilities of behavioral state transitions measured from experimental recordings of rat sleep under ad libitum conditions and after 24 h of REM sleep deprivation. Reliable transitions from REM sleep to wake, as dictated by the data, indicated the necessity of an excitatory projection from the REM-on population to the wake-promoting population. To replicate the increase in REM-wake-REM transitions observed after 24 h REM sleep deprivation required that this excitatory projection promote transient activation of the wake-promoting population. Obtaining the reliable wake-nonREM sleep transitions observed in the data required that activity of the wake-promoting population modulated the interaction between the REM-on and REM-off populations. This analysis suggests neuronal processes to be targeted in further experimental studies of the regulatory mechanisms of REM sleep.

The ground and low-lying excited states and feasibility of laser cooling for GaH+ and InH+ cations

NASA Astrophysics Data System (ADS)

Zhang, Qing-Qing; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang

2018-03-01

The potential energy curves and transition dipole moments of 12Σ+ and 12Π states of GaH+ and InH+ cations are performed by employing ab initio calculations. Based on the potential energy curves, the rotational and vibrational energy levels of the two states are obtained by solving the Schrödinger equation of nuclear movement. The spectroscopic parameters are deduced with the obtained rovibrational energy levels. The spin-orbit coupling effect of the 2Π states for both the GaH+ and InH+ cations are also calculated. The feasibility of laser cooling of GaH+ and InH+ cations are examined by using the results of the electronic and spectroscopic properties. The highly diagonal Franck-Condon factors and appropriate radiative lifetimes are determined by using the potential energy curves and transition dipole moments for the 2Π1/2, 3/2 ↔ 12Σ+ transitions. The results indicate that the 2Π1/2, 3/2 ↔ 12Σ+ transitions of both GaH+ and InH+ cations are appropriate for the close cycle transition of laser cooling. The optical scheme of the laser cooling is constructed for the GaH+ and InH+ cations.

Convergent and parallel evolution in life habit of the scallops (Bivalvia: Pectinidae)

PubMed Central

2011-01-01

Background We employed a phylogenetic framework to identify patterns of life habit evolution in the marine bivalve family Pectinidae. Specifically, we examined the number of independent origins of each life habit and distinguished between convergent and parallel trajectories of life habit evolution using ancestral state estimation. We also investigated whether ancestral character states influence the frequency or type of evolutionary trajectories. Results We determined that temporary attachment to substrata by byssal threads is the most likely ancestral condition for the Pectinidae, with subsequent transitions to the five remaining habit types. Nearly all transitions between life habit classes were repeated in our phylogeny and the majority of these transitions were the result of parallel evolution from byssate ancestors. Convergent evolution also occurred within the Pectinidae and produced two additional gliding clades and two recessing lineages. Furthermore, our analysis indicates that byssal attaching gave rise to significantly more of the transitions than any other life habit and that the cementing and nestling classes are only represented as evolutionary outcomes in our phylogeny, never as progenitor states. Conclusions Collectively, our results illustrate that both convergence and parallelism generated repeated life habit states in the scallops. Bias in the types of habit transitions observed may indicate constraints due to physical or ontogenetic limitations of particular phenotypes. PMID:21672233

High-Resolution Study of the Perturbation in the CO Triplet Band

NASA Astrophysics Data System (ADS)

Momona, M.; Kanamori, H.; Sakurai, K.

1993-05-01

Seven hundred absorption lines have been observed in the discharge plasma of He and CO in the 12600-12 800 cm-1 region with Doppler-limited resolution by a near-infrared diode laser spectrometer. Out of complex spectral patterns, more than 400 lines were assigned to the CO triplet band, d3Δ(v‧ = 2) - a3Π (v″ = 1). The upper state of this transition is known to be severely perturbed. The measurement of all the spin subbands of the 3Δ - 3Π transition allowed us to reanalyze the perturbation of the d3Δ (v = 2) state with the highly vibrationally excited state, v = 9, in the a3Π state. Diode laser spectroscopy with high sensitivity and Doppler-limited resolution revealed the overtone band transition from v = 1 to v = 9 within the a3Π state and the Λ-type doubling in the d3Δ state. Those interesting phenomena can be understood as a result of the perturbation and were successfully reproduced by the eigenvectors determined in this analysis.

State-selective optimization of local excited electronic states in extended systems

NASA Astrophysics Data System (ADS)

Kovyrshin, Arseny; Neugebauer, Johannes

2010-11-01

Standard implementations of time-dependent density-functional theory (TDDFT) for the calculation of excitation energies give access to a number of the lowest-lying electronic excitations of a molecule under study. For extended systems, this can become cumbersome if a particular excited state is sought-after because many electronic transitions may be present. This often means that even for systems of moderate size, a multitude of excited states needs to be calculated to cover a certain energy range. Here, we present an algorithm for the selective determination of predefined excited electronic states in an extended system. A guess transition density in terms of orbital transitions has to be provided for the excitation that shall be optimized. The approach employs root-homing techniques together with iterative subspace diagonalization methods to optimize the electronic transition. We illustrate the advantages of this method for solvated molecules, core-excitations of metal complexes, and adsorbates at cluster surfaces. In particular, we study the local π →π∗ excitation of a pyridine molecule adsorbed at a silver cluster. It is shown that the method works very efficiently even for high-lying excited states. We demonstrate that the assumption of a single, well-defined local excitation is, in general, not justified for extended systems, which can lead to root-switching during optimization. In those cases, the method can give important information about the spectral distribution of the orbital transition employed as a guess.

40 CFR 70.4 - State program submittals and transition.

Code of Federal Regulations, 2013 CFR

2013-07-01

... determine insignificant activities or emission levels for purposes of determining complete applications... any permit application, compliance plan, permit, and monitoring and compliance, certification report... take final action on an application for a permit, permit renewal, or permit revision within the time...

40 CFR 70.4 - State program submittals and transition.

Code of Federal Regulations, 2014 CFR

2014-07-01

... determine insignificant activities or emission levels for purposes of determining complete applications... any permit application, compliance plan, permit, and monitoring and compliance, certification report... take final action on an application for a permit, permit renewal, or permit revision within the time...

40 CFR 70.4 - State program submittals and transition.

Code of Federal Regulations, 2012 CFR

2012-07-01

... determine insignificant activities or emission levels for purposes of determining complete applications... any permit application, compliance plan, permit, and monitoring and compliance, certification report... take final action on an application for a permit, permit renewal, or permit revision within the time...

Design of biomimetic catalysts by molecular imprinting in synthetic polymers: the role of transition state stabilization.

PubMed

Wulff, Günter; Liu, Junqiu

2012-02-21

The impressive efficiency and selectivity of biological catalysts has engendered a long-standing effort to understand the details of enzyme action. It is widely accepted that enzymes accelerate reactions through their steric and electronic complementarity to the reactants in the rate-determining transition states. Thus, tight binding to the transition state of a reactant (rather than to the corresponding substrate) lowers the activation energy of the reaction, providing strong catalytic activity. Debates concerning the fundamentals of enzyme catalysis continue, however, and non-natural enzyme mimics offer important additional insight in this area. Molecular structures that mimic enzymes through the design of a predetermined binding site that stabilizes the transition state of a desired reaction are invaluable in this regard. Catalytic antibodies, which can be quite active when raised against stable transition state analogues of the corresponding reaction, represent particularly successful examples. Recently, synthetic chemistry has begun to match nature's ability to produce antibody-like binding sites with high affinities for the transition state. Thus, synthetic, molecularly imprinted polymers have been engineered to provide enzyme-like specificity and activity, and they now represent a powerful tool for creating highly efficient catalysts. In this Account, we review recent efforts to develop enzyme models through the concept of transition state stabilization. In particular, models for carboxypeptidase A were prepared through the molecular imprinting of synthetic polymers. On the basis of successful experiments with phosphonic esters as templates to arrange amidinium groups in the active site, the method was further improved by combining the concept of transition state stabilization with the introduction of special catalytic moieties, such as metal ions in a defined orientation in the active site. In this way, the imprinted polymers were able to provide both an electrostatic stabilization for the transition state through the amidinium group as well as a synergism of transition state recognition and metal ion catalysis. The result was an excellent catalyst for carbonate hydrolysis. These enzyme mimics represent the most active catalysts ever prepared through the molecular imprinting strategy. Their catalytic activity, catalytic efficiency, and catalytic proficiency clearly surpass those of the corresponding catalytic antibodies. The active structures in natural enzymes evolve within soluble proteins, typically by the refining of the folding of one polypeptide chain. To incorporate these characteristics into synthetic polymers, we used the concept of transition state stabilization to develop soluble, nanosized carboxypeptidase A models using a new polymerization method we term the "post-dilution polymerization method". With this methodology, we were able to prepare soluble, highly cross-linked, single-molecule nanoparticles. These particles have controlled molecular weights (39 kDa, for example) and, on average, one catalytically active site per particle. Our strategies have made it possible to obtain efficient new enzyme models and further advance the structural and functional analogy with natural enzymes. Moreover, this bioinspired design based on molecular imprinting in synthetic polymers offers further support for the concept of transition state stabilization in catalysis.

Role of the Disulfide Bond in Prion Protein Amyloid Formation: A Thermodynamic and Kinetic Analysis.

PubMed

Honda, Ryo

2018-02-27

Prion diseases are associated with the structural conversion of prion protein (PrP) to a β-sheet-rich aggregate, PrP Sc . Previous studies have indicated that a reduction of the disulfide bond linking C179 and C214 of PrP yields an amyloidlike β-rich aggregate in vitro. To gain mechanistic insights into the reduction-induced aggregation, here I characterized how disulfide bond reduction modulates the protein folding/misfolding landscape of PrP, by examining 1) the equilibrium stabilities of the native (N) and aggregated states relative to the unfolded (U) state, 2) the transition barrier separating the U and aggregated states, and 3) the final structure of amyloidlike misfolded aggregates. Kinetic and thermodynamic experiments revealed that disulfide bond reduction decreases the equilibrium stabilities of both the N and aggregated states by ∼3 kcal/mol, without changing either the amyloidlike aggregate structure, at least at the secondary structural level, or the transition barrier of aggregation. Therefore, disulfide bond reduction modulates the protein folding/misfolding landscape by entropically stabilizing disordered states, including the U and transition state of aggregation. This also indicates that the equilibrium stability of the N state, but not the transition barrier of aggregation, is the dominant factor determining the reduction-induced aggregation of PrP. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Stationary to nonstationary transition in crossed-field devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marini, Samuel; Rizzato, Felipe B.; Pakter, Renato

2016-03-15

The previous results based on numerical simulations showed that a cold electron beam injected in a crossed field gap does not reach a time independent stationary state in the space charge limited regime [P. J. Christenson and Y. Y. Lau, Phys. Plasmas 1, 3725 (1994)]. In this work, the effect of finite injection temperature in the transition from stationary to nonstationary states is investigated. A fully kinetic model for the electron flow is derived and used to determine the possible stationary states of the system. It is found that although there is always a stationary solution for any set ofmore » parameters, depending on the injection temperature the electron flow becomes very sensitive to fluctuations and the stationary state is never reached. By investigating the nonlinear dynamics of a characteristic electron, a theory based on a single free parameter is constructed to predict when the transition between stationary and nonstationary states occurs. In agreement with the previous numerical results, the theory indicates that for vanishing temperatures the system never reaches the time independent stationary state in the space charge limited regime. Nevertheless, as the injection temperature is raised it is found a broad range of system parameters for which the stationary state is indeed attained. By properly adjusting the free parameter in the theory, one can be able to describe, to a very good accuracy, when the transition occurs.« less

Redundant Information and the Quantum-Classical Transition

ERIC Educational Resources Information Center

Riedel, Charles Jess

2012-01-01

A state selected at random from the Hilbert space of a many-body system is overwhelmingly likely to exhibit highly non-classical correlations. For these typical states, half of the environment must be measured by an observer to determine the state of a given subsystem. The objectivity of classical reality--the fact that multiple observers can each…

An ab initio study of the low-lying doublet states of AgO and AgS

NASA Astrophysics Data System (ADS)

Bauschlicher, Charles W.; Partridge, Harry; Langhoff, Stephen R.

1990-11-01

Spectroscopic constants ( Do, re, μ e, Te) are determined for the doublet states of AgO and AgS below ≈ 30000 cm -1. valence basis sets are employed in conjunction with relativistic effective core potentials (RECPs). Electron correlation is included using the modified coupled-pair functional (MCPF) and multireferenceconfiguration interaction (MRCI) methods. The A 2Σ +-X 2Π band system is found to occur in the near infrared ( ≈ 9000 cm -1) and to be relatively weak with a radiative lifetime of 900 μs for A 2Σ + (ν = 0). The weakly bound C 2Π state (our notation), the upper state of the blue system, is found to require high levels of theoretical treatment to determine a quantitatively accurate potential. The red system is assigned as a transition from the C 2Π state to the previously unobserved A 2Σ + state. Several additional transitions are identified that should be detectable experiment A more limited study is performed for the vertical excitation spectrum of AgS. In addition, a detailed all-electron study of the X 2Π and A 2Σ + states of AgO is carried out using large atomic natural orbital (ANO) basis sets. Our best calculated Do value for AgO is significantly less than the experimental value, which suggests that there may be some systematic error in the experimental determination.

Tunable ion-photon entanglement in an optical cavity.

PubMed

Stute, A; Casabone, B; Schindler, P; Monz, T; Schmidt, P O; Brandstätter, B; Northup, T E; Blatt, R

2012-05-23

Proposed quantum networks require both a quantum interface between light and matter and the coherent control of quantum states. A quantum interface can be realized by entangling the state of a single photon with the state of an atomic or solid-state quantum memory, as demonstrated in recent experiments with trapped ions, neutral atoms, atomic ensembles and nitrogen-vacancy spins. The entangling interaction couples an initial quantum memory state to two possible light-matter states, and the atomic level structure of the memory determines the available coupling paths. In previous work, the transition parameters of these paths determined the phase and amplitude of the final entangled state, unless the memory was initially prepared in a superposition state (a step that requires coherent control). Here we report fully tunable entanglement between a single (40)Ca(+) ion and the polarization state of a single photon within an optical resonator. Our method, based on a bichromatic, cavity-mediated Raman transition, allows us to select two coupling paths and adjust their relative phase and amplitude. The cavity setting enables intrinsically deterministic, high-fidelity generation of any two-qubit entangled state. This approach is applicable to a broad range of candidate systems and thus is a promising method for distributing information within quantum networks.

Electronic Transitions of Tungsten Monosulfide

NASA Astrophysics Data System (ADS)

Tsang, L. F.; Chan, Man-Chor; Zou, Wenli; Cheung, Allan S. C.

2017-06-01

Electronic transition spectrum of the tungsten monosulfide (WS) molecule in the near infrared region between 725 nm and 885 nm has been recorded using laser ablation/reaction free-jet expansion and laser induced fluorescence spectroscopy. The WS molecule was produced by reacting laser - ablated tungsten atoms with 1% CS_{2} seeded in argon. Fifteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transition systems. The ground state has been identified to be the X^{3}Σ^{-}(0^{+}) state, and the determined vibrational frequency, ΔG_{1/2} and bond length, r_{0}, are respectively 556.7 cm^{-1} and 2.0676 Å. In addition, vibrational bands belong to another transition system involving lower state with Ω = 1 component have also been analyzed. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The low-lying Λ-S states and Ω sub-states of WS have been calculated using state-averaged complete active space self-consistent field (SA-CASSCF) and followed by MRCISD+Q (internally contracted multi-reference configuration interaction with singles and doubles plus Davidson's cluster correction). The active space consists of 10 electrons in 9 orbitals corresponding to the W 5d6s and S 3p shells. The lower molecular orbitals from W 5s5p and S 3s are inactive but are also correlated, and relativistic effective core potential (RECPs) are adopted to replace the core orbitals with 60 (W) and 10 (S) core electrons, respectively. Spin-orbit coupling (SOC) is calculated via the state-interaction (SI) approach with RECP spin-orbit operators using SA-CASSCF wavefunctions, where the diagonal elements in the SOC matrix are replaced by the corresponding MRCISD+Q energies calculated above. Spectroscopic constants and potential energy curves of the ground and many low-lying Λ-S states and Ω sub-states of the WS molecule are obtained. The calculated spectroscopic constants of the ground and low-lying states are generally in good agreement with our experimental determination. This work represents the first experimental investigation of the electronic and molecular structure of the WS molecule.

Magic wavelengths of the Ca+ ion for circularly polarized light

NASA Astrophysics Data System (ADS)

Jiang, Jun; Jiang, Li; Wang, Xia; Zhang, Deng-Hong; Xie, Lu-You; Dong, Chen-Zhong

2017-10-01

The dynamic dipole polarizabilities of low-lying states of Ca+ ions for circularly polarized light are calculated by using the relativistic configuration interaction plus core polarization approach. The magic wavelengths are determined for the magnetic sublevel transitions 4 s1/2 ,m→4 pj',m' and 4 s1/2 ,m→3 dj',m' with total angular momentum j' and its components m'. In contrast to the case of linearly polarized light, several additional magic wavelengths are found for these transitions. We suggest that accurate measurements on the magic wavelengths near 851 nm for the 4 s1/2 ,m→4 p3/2 ,m' transitions can be used to determine the ratio of the oscillator strengths for the 4 p3/2→3 d3/2 and 4 p3/2→3 d5/2 transitions.

Physiologic Measures of Animal Stress during Transitional States of Consciousness

PubMed Central

Meyer, Robert E.

2015-01-01

Simple Summary The humaneness, and therefore suitability, of any particular agent or method used to produce unconsciousness in animals, whether for anesthesia, euthanasia, humane slaughter, or depopulation, depends on the experience of pain or distress prior to loss of consciousness. Commonly reported physiologic measures of animal stress, including physical movement and vocalization, heart rate and ECG, electroencephalographic activity, and plasma and neuronal stress markers are discussed within this context. Abstract Determination of the humaneness of methods used to produce unconsciousness in animals, whether for anesthesia, euthanasia, humane slaughter, or depopulation, relies on our ability to assess stress, pain, and consciousness within the contexts of method and application. Determining the subjective experience of animals during transitional states of consciousness, however, can be quite difficult; further, loss of consciousness with different agents or methods may occur at substantially different rates. Stress and distress may manifest behaviorally (e.g., overt escape behaviors, approach-avoidance preferences [aversion]) or physiologically (e.g., movement, vocalization, changes in electroencephalographic activity, heart rate, sympathetic nervous system [SNS] activity, hypothalamic-pituitary axis [HPA] activity), such that a one-size-fits-all approach cannot be easily applied to evaluate methods or determine specific species applications. The purpose of this review is to discuss methods of evaluating stress in animals using physiologic methods, with emphasis on the transition between the conscious and unconscious states. PMID:26479382

Evidence for a first-order liquid-liquid transition in high-pressure hydrogen from ab initio simulations.

PubMed

Morales, Miguel A; Pierleoni, Carlo; Schwegler, Eric; Ceperley, D M

2010-07-20

Using quantum simulation techniques based on either density functional theory or quantum Monte Carlo, we find clear evidence of a first-order transition in liquid hydrogen, between a low conductivity molecular state and a high conductivity atomic state. Using the temperature dependence of the discontinuity in the electronic conductivity, we estimate the critical point of the transition at temperatures near 2,000 K and pressures near 120 GPa. Furthermore, we have determined the melting curve of molecular hydrogen up to pressures of 200 GPa, finding a reentrant melting line. The melting line crosses the metalization line at 700 K and 220 GPa using density functional energetics and at 550 K and 290 GPa using quantum Monte Carlo energetics.

Fast-timing lifetime measurements of excited states in Cu67

NASA Astrophysics Data System (ADS)

NiÅ£ǎ, C. R.; Bucurescu, D.; Mǎrginean, N.; Avrigeanu, M.; Bocchi, G.; Bottoni, S.; Bracco, A.; Bruce, A. M.; Cǎta-Danil, G.; Coló, G.; Deleanu, D.; Filipescu, D.; GhiÅ£ǎ, D. G.; Glodariu, T.; Leoni, S.; Mihai, C.; Mason, P. J. R.; Mǎrginean, R.; Negret, A.; Pantelicǎ, D.; Podolyak, Z.; Regan, P. H.; Sava, T.; Stroe, L.; Toma, S.; Ur, C. A.; Wilson, E.

2014-06-01

The half-lives of the 9/2+, 13/2+, and 15/2+ yrast states in the neutron-rich Cu67 nucleus were determined by using the in-beam fast-timing technique. The experimentally deduced E3 transition strength for the decay of the 9/2+ level to the 3/2- ground state indicates that the wave function of this level might contain a collective component arising from the coupling of the odd proton p3/2 with the 3- state in Ni66. Theoretical interpretations of the 9/2+ state are presented within the particle-vibration weak-coupling scheme involving the unpaired proton and the 3- state from Ni66 and within shell-model calculations with a Ni56 core using the jj44b residual interaction. The shell model also accounts reasonably well for the other measured electromagnetic transition probabilities.

Transition States and transition state analogue interactions with enzymes.

PubMed

Schramm, Vern L

2015-04-21

Enzymatic transition states have lifetimes of a few femtoseconds (fs). Computational analysis of enzyme motions leading to transition state formation suggests that local catalytic site motions on the fs time scale provide the mechanism to locate transition states. An experimental test of protein fs motion and its relation to transition state formation can be provided by isotopically heavy proteins. Heavy enzymes have predictable mass-altered bond vibration states without altered electrostatic properties, according to the Born-Oppenheimer approximation. On-enzyme chemistry is slowed in most heavy proteins, consistent with altered protein bond frequencies slowing the search for the transition state. In other heavy enzymes, structural changes involved in reactant binding and release are also influenced. Slow protein motions associated with substrate binding and catalytic site preorganization are essential to allow the subsequent fs motions to locate the transition state and to facilitate the efficient release of products. In the catalytically competent geometry, local groups move in stochastic atomic motion on the fs time scale, within transition state-accessible conformations created by slower protein motions. The fs time scale for the transition state motions does not permit thermodynamic equilibrium between the transition state and stable enzyme states. Isotopically heavy enzymes provide a diagnostic tool for fast coupled protein motions to transition state formation and mass-dependent conformational changes. The binding of transition state analogue inhibitors is the opposite in catalytic time scale to formation of the transition state but is related by similar geometries of the enzyme-transition state and enzyme-inhibitor interactions. While enzymatic transition states have lifetimes as short as 10(-15) s, transition state analogues can bind tightly to enzymes with release rates greater than 10(3) s. Tight-binding transition state analogues stabilize the rare but evolved enzymatic geometry to form the transition state. Evolution to efficient catalysis optimized this geometry and its stabilization by a transition state mimic results in tight binding. Release rates of transition state analogues are orders of magnitude slower than product release in normal catalytic function. During catalysis, product release is facilitated by altered chemistry. Compared to the weak associations found in Michaelis complexes, transition state analogues involve strong interactions related to those in the transition state. Optimum binding of transition state analogues occurs when the complex retains the system motions intrinsic to transition state formation. Conserved dynamic motion retains the entropic components of inhibitor complexes, improving the thermodynamics of analogue binding.

Fine structure and lifetime of dark excitons in transition metal dichalcogenide monolayers

NASA Astrophysics Data System (ADS)

Robert, C.; Amand, T.; Cadiz, F.; Lagarde, D.; Courtade, E.; Manca, M.; Taniguchi, T.; Watanabe, K.; Urbaszek, B.; Marie, X.

2017-10-01

The intricate interplay between optically dark and bright excitons governs the light-matter interaction in transition metal dichalcogenide monolayers. We have performed a detailed investigation of the "spin-forbidden" dark excitons in WSe2 monolayers by optical spectroscopy in an out-of-plane magnetic field Bz. In agreement with the theoretical predictions deduced from group theory analysis, magnetophotoluminescence experiments reveal a zero-field splitting δ =0.6 ±0.1 meV between two dark exciton states. The low-energy state is strictly dipole forbidden (perfectly dark) at Bz=0 , while the upper state is partially coupled to light with z polarization ("gray" exciton). The first determination of the dark neutral exciton lifetime τD in a transition metal dichalcogenide monolayer is obtained by time-resolved photoluminescence. We measure τD˜110 ±10 ps for the gray exciton state, i.e., two orders of magnitude longer than the radiative lifetime of the bright neutral exciton at T =12 K .

Lifetime measurements of 17C excited states and three-body and continuum effects

DOE PAGES

Smalley, D.; Iwasaki, H.; Navratil, P.; ...

2015-12-18

We studied transition rates for the lowest 1/2 + and 5/2 + excited states of 17C through lifetime measurements with the GRETINA array using the recoil-distance method. The present measurements provide a model-independent determination of transition strengths giving the values of B(M1;1/2 + → 3/2 + g.s.) = 1.04 +0.03 –0.12 × 1 0–2μ 2 N and B(M1;5/2 + → 3/2 + g.s.) = 7.12 +1.27 –0.96 × 10 –2μ 2 N. The quenched M1 transition strength for the 1/2 + → 3/2 + g.s. transition, with respect to the 5/2 + → 3/ 2+ g.s. transition, has been confirmedmore » with greater precision. Furthermore, the current data are compared to importance-truncated no-core shell model calculations addressing effects due to continuum and three-body forces.« less

Simulation of the A-X and B-X transition emission spectra of the InBr molecule for diagnostics in low-pressure plasmas

NASA Astrophysics Data System (ADS)

Briefi, S.; Fantz, U.

2011-04-01

Inductively coupled low-pressure discharges containing InBr have been investigated spectroscopically. In order to obtain plasma parameters such as the vibrational and rotational temperature of the InBr molecule, the emission spectra of the A\\,^3\\!\\Pi_{0^+}\\rightarrow X\\,^1\\!\\Sigma_{0}^+ and the B\\,^3\\! \\Pi_{1}\\rightarrow X\\,^1\\!\\Sigma_{0}^+ transitions have been simulated. The program is based on the molecular constants and takes into account vibrational states up to v = 24. The required Franck-Condon factors and vibrationally resolved transition probabilities have been computed solving the Schrödinger equation using the Born-Oppenheimer approximation. The ground state density of the InBr molecule in the plasma has been determined from absorption spectra using effective transition probabilities for the A-X and B-X transition according to the vibrational population. The obtained densities agree well with densities derived from an Arrhenius type vapour pressure equation.

Imaging metal-like monoclinic phase stabilized by surface coordination effect in vanadium dioxide nanobeam

PubMed Central

Li, Zejun; Wu, Jiajing; Hu, Zhenpeng; Lin, Yue; Chen, Qi; Guo, Yuqiao; Liu, Yuhua; Zhao, Yingcheng; Peng, Jing; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2017-01-01

In correlated systems, intermediate states usually appear transiently across phase transitions even at the femtosecond scale. It therefore remains an open question how to determine these intermediate states—a critical issue for understanding the origin of their correlated behaviour. Here we report a surface coordination route to successfully stabilize and directly image an intermediate state in the metal-insulator transition of vanadium dioxide. As a prototype metal-insulator transition material, we capture an unusual metal-like monoclinic phase at room temperature that has long been predicted. Coordinate bonding of L-ascorbic acid molecules with vanadium dioxide nanobeams induces charge-carrier density reorganization and stabilizes metallic monoclinic vanadium dioxide, unravelling orbital-selective Mott correlation for gap opening of the vanadium dioxide metal–insulator transition. Our study contributes to completing phase-evolution pathways in the metal-insulator transition process, and we anticipate that coordination chemistry may be a powerful tool for engineering properties of low-dimensional correlated solids. PMID:28613281

Effective collision strengths for the electron impact excitation of Mg

NASA Astrophysics Data System (ADS)

Hudson, C. E.; Ramsbottom, C. A.; Norrington, P. H.; Scott, M. P.

2008-05-01

Electron impact excitation collision strengths for fine structure transitions of Mg,have been determined by a Breit-Pauli R-matrix calculation. The target states are represented by configuration interaction wavefunctions and consist of the 19 lowest LS states, having configurations 2s^22p^4, 2s2p^5, 2p^6, 2s^22p^33s and 2s^22p^33p. These target states give rise to 37 fine structure levels and 666 possible transitions. The effective collision strengths are calculated by averaging the electron collision strengths over a Maxwellian distribution of electron velocities. Effective collision strengths for transitions between the fine structure levels are given for electron temperatures in the range 10Te(K) = 3.0 - 7.0. Results are compared with the previous R-matrix calculation of Butler & Zeippen (AASS, 1994) and the recent Distorted Wave evaluations of Bhatia, Landi & Eissner (ADNDT, 2006).

The A6Sigma+ - X6Sigma+ Transition of CrH, Einstein Coefficients and an Improved Description of the A State

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Ram, R. S.; Bernath, Peter F.; Parsons, C. G.; Galehouse, D.; Arnold, James O. (Technical Monitor)

2001-01-01

The spectrum of CrH has been reinvestigated in the 9000-15000/cm region using the Fourier transform spectrometer of the National Solar Observatory. The 1-0 and 1-1 bands of the A6Sigma+ - X6Sigma+ transition have been measured and improved spectroscopic constants have been determined. A value for the 2-0 band origin has been obtained from the band head using estimated spectroscopic constants. These data provide a set of much improved equilibrium vibrational and rotational constants for the A6Sigma+ state. An accurate description of the A-X transition has been obtained using a multi-reference configuration interaction approach. The inclusion of both scalar relativity and Cr 3s3p correlation are required to obtain a good description of both states. The ab initio computed Einstein coefficients and radiative lifetimes are reported.

Steady-state and transitional aerodynamic characteristics of a wing in simulated heavy rain

NASA Technical Reports Server (NTRS)

Campbell, Bryan A.; Bezos, Gaudy M.

1989-01-01

The steady-state and transient effects of simulated heavy rain on the subsonic aerodynamic characteristics of a wing model were determined in the Langley 14- by 22-Foot Subsonic Tunnel. The 1.29 foot chord wing was comprised of a NACA 23015 airfoil and had an aspect ratio of 6.10. Data were obtained while test variables of liquid water content, angle of attack, and trailing edge flap angle were parametrically varied at dynamic pressures of 10, 30, and 50 psf (i.e., Reynolds numbers of .76x10(6), 1.31x10(6), and 1.69x10(6)). The experimental results showed reductions in lift and increases in drag when in the simulated rain environment. Accompanying this was a reduction of the stall angle of attack by approximately 4 deg. The transient aerodynamic performance during transition from dry to wet steady-state conditions varied between a linear and a nonlinear transition.

Theoretical study of metal noble-gas positive ions

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.

1989-01-01

Theoretical calculations have been performed to determine the spectroscopic constant for the ground and selected low-lying electronic states of the transition-metal noble-gas ions Var(+), FeAr(+), CoAr(+), CuHe(+), CuAr(+), and CuKr(+). Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr(+), LiKr(+), NaAr(+), and KAr(+) and the alkaline-earth noble-gas ion MgAr(+) to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. It is found that the spectroscopic constants of the X 1Sigma(+) states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation.

Kinetics from Replica Exchange Molecular Dynamics Simulations.

PubMed

Stelzl, Lukas S; Hummer, Gerhard

2017-08-08

Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.

Near Infrared Laser Spectroscopy of Scandium Monobromide

NASA Astrophysics Data System (ADS)

Xia, Ye; Cheung, A. S.-C.; Liao, Zhenwu; Yang, Mei; Chan, Man-Chor

2012-06-01

High resolution laser spectrum of scandium monobromide (ScBr) between 787 and 845 nm has been investigated using the technique of laser vaporization/reaction with free jet expansion and laser induced fluorescence spectroscopy. ScBr was produced by reacting laser vaporized Sc atoms with ethyl bromide (C2H5Br). Spectra of six vibrational bands of both Sc79Br and Sc81Br isotopomers of the C1 Σ+ - X1 Σ+ transition and seven vibrational bands of the e3 Δ - a3 Δ transition were obtained and analyzed. Least-squares fit of the measured line positions for the singlet transitions yielded accurate molecular constants for the v = 0 - 3 levels of the C1 Σ+ state and the v = 0 - 2 levels of the X1 Σ+ state. Similar least-squares fit for the triplet transitions yielded molecular constants for the v = 0 - 2 levels of both e3 Δ and a3 Δ states. The equilibrium bond length, r_0, of the a3 Δ state has been determined to be 2.4789 Å. Financial support from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. HKU 701008P) is gratefully acknowledged

Pseudo-direct bandgap transitions in silicon nanocrystals: effects on optoelectronics and thermoelectrics.

PubMed

Singh, Vivek; Yu, Yixuan; Sun, Qi-C; Korgel, Brian; Nagpal, Prashant

2014-12-21

While silicon nanostructures are extensively used in electronics, the indirect bandgap of silicon poses challenges for optoelectronic applications like photovoltaics and light emitting diodes (LEDs). Here, we show that size-dependent pseudo-direct bandgap transitions in silicon nanocrystals dominate the interactions between (photoexcited) charge carriers and phonons, and hence the optoelectronic properties of silicon nanocrystals. Direct measurements of the electronic density of states (DOS) for different sized silicon nanocrystals reveal that these pseudo-direct transitions, likely arising from the nanocrystal surface, can couple with the quantum-confined silicon states. Moreover, we demonstrate that since these transitions determine the interactions of charge carriers with phonons, they change the light emission, absorption, charge carrier diffusion and phonon drag (Seebeck coefficient) in nanoscaled silicon semiconductors. Therefore, these results can have important implications for the design of optoelectronics and thermoelectric devices based on nanostructured silicon.

The dynamics of the optically driven Lambda transition of the 15N-V- center in diamond.

PubMed

González, Gabriel; Leuenberger, Michael N

2010-07-09

Recent experimental results demonstrate the possibility of writing quantum information in the ground state triplet of the (15)N-V(-) center in diamond by means of an optically driven spin non-conserving two-photon Lambda transition in the presence of a strong applied electric field. Our calculations show that the hyperfine interaction in the (15)N-V(-) center is capable of mediating such a transition. We use a density matrix approach to describe the exact dynamics for the allowed optical spin non-conserving transitions between two sublevels of the ground state triplet. This approach allows us to calculate the Rabi oscillations, by means of which we obtain a Rabi frequency with an upper bound determined by the hyperfine interaction. This result is crucial for the success of implementing optically driven quantum information processing with the N-V center in diamond.

Magnetic structure of NiS2 -xSex

NASA Astrophysics Data System (ADS)

Yano, S.; Louca, Despina; Yang, J.; Chatterjee, U.; Bugaris, D. E.; Chung, D. Y.; Peng, L.; Grayson, M.; Kanatzidis, Mercouri G.

2016-01-01

NiS2 -2 xSex is revisited to determine the magnetic structure using neutron diffraction and magnetic representational analysis. Upon cooling, the insulating parent compound, NiS2, becomes antiferromagnetic with two successive magnetic transitions. The first transition (M 1 ) occurs at TN˜39 K with Γ1ψ1 symmetry and a magnetic propagation vector of k =(000 ) . The second transition (M 2 ) occurs at TN˜30 K with k =(0.5 ,0.5 ,0.5 ) and a Γ1ψ2 symmetry with face-centered translations, giving rise to four possible magnetic domains. With doping, the system becomes metallic. The transition to the M 2 state is suppressed prior to x =0.4 while the M 1 state persists. The M 1 magnetic structure gradually vanishes by x ˜0.8 at a lower concentration than previously reported. The details of the magnetic structures are provided.

Ultraviolet laser spectroscopy of jet-cooled CaNC and SrNC free radicals: Observation of bent excited electronic states

NASA Astrophysics Data System (ADS)

Greetham, Gregory M.; Ellis, Andrew M.

2000-11-01

New electronic transitions of the CaNC and SrNC free radicals have been identified in the near ultraviolet. For CaNC one new system, labeled the D˜-X˜ transition, was observed in the 31 500-33 400 cm-1 region. Two new transitions were found for SrNC, the D˜-X˜ and Ẽ-X˜ systems spanning 29 100-31 000 and 32 750-34 000 cm-1, respectively. Jet-cooled laser excitation spectra yield complex vibrational structure, much of which is attributed to excitation of the bending vibration. This has been used to infer that the molecule adopts a nonlinear equilibrium geometry in the upper electronic state in all three band systems, in contrast to the linear ground electronic state. This structural change is accounted for by the increased diffuseness of the unpaired electron in the excited states, which favors deviation from linearity. All three new excited states are assigned 2A' symmetry and correlate with 2Σ+ states in the linear molecule limit. Tentative estimates for the barriers to linearity in the D˜ 2A' states of CaNC and SrNC have been determined as ˜700 and ˜1050 cm-1, respectively.

Glucose turnover in kelp bass (Paralabrax sp. ): in vivo studies with (6-/sup 3/H,6-/sup 14/C)glucose

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bever, K.; Chenoweth, M.; Dunn, A.

1977-01-01

(6-/sup 3/H,6-/sup 14/C)glucose was injected via an indwelling arterial cannula in free-swimming, fed, and fasted kelp bass to determine hepatic glucose production, peripheral glucose uptake, minimal glucose mass, mean transit time, and the percent of carbon recycling under the two different nutritional states. Mean plasma glucose levels remained unchanged in fed and fasted fish (48 +- 8 vs. 43 +- 8 mg/100 ml). During steady-state conditions, glucose replacement rates of fed and fasted fish determined with (6-/sup 3/H)glucose are similar (0.035 +- 0.006 vs. 0.025 +- 0.003 mg/min per 100 g) and do not differ from rates determined with (6-/supmore » 14/C)glucose (0.035 +- 0.005 vs. 0.026 +- 0.002). The minimal glucose masses and the mean transit times determined with both isotopes are also similar suggesting that plasma glucose levels and glucose turnover are maintained in fish fasted up to 40 days with no apparent increase in carbon recycling. Nonsteady-state isotope experiments suggest that these fish can alter rates of hepatic glucose production and peripheral uptake in response to hyper- and hypoglycemia.« less

3-D High-Lift Flow-Physics Experiment - Transition Measurements

NASA Technical Reports Server (NTRS)

McGinley, Catherine B.; Jenkins, Luther N.; Watson, Ralph D.; Bertelrud, Arild

2005-01-01

An analysis of the flow state on a trapezoidal wing model from the NASA 3-D High Lift Flow Physics Experiment is presented. The objective of the experiment was to characterize the flow over a non-proprietary semi-span three-element high-lift configuration to aid in assessing the state of the art in the computation of three-dimensional high-lift flows. Surface pressures and hot-film sensors are used to determine the flow conditions on the slat, main, and flap. The locations of the attachments lines and the values of the attachment line Reynolds number are estimated based on the model surface pressures. Data from the hot-films are used to determine if the flow is laminar, transitional, or turbulent by examining the hot-film time histories, statistics, and frequency spectra.

Dynamic Histogram Analysis To Determine Free Energies and Rates from Biased Simulations.

PubMed

Stelzl, Lukas S; Kells, Adam; Rosta, Edina; Hummer, Gerhard

2017-12-12

We present an algorithm to calculate free energies and rates from molecular simulations on biased potential energy surfaces. As input, it uses the accumulated times spent in each state or bin of a histogram and counts of transitions between them. Optimal unbiased equilibrium free energies for each of the states/bins are then obtained by maximizing the likelihood of a master equation (i.e., first-order kinetic rate model). The resulting free energies also determine the optimal rate coefficients for transitions between the states or bins on the biased potentials. Unbiased rates can be estimated, e.g., by imposing a linear free energy condition in the likelihood maximization. The resulting "dynamic histogram analysis method extended to detailed balance" (DHAMed) builds on the DHAM method. It is also closely related to the transition-based reweighting analysis method (TRAM) and the discrete TRAM (dTRAM). However, in the continuous-time formulation of DHAMed, the detailed balance constraints are more easily accounted for, resulting in compact expressions amenable to efficient numerical treatment. DHAMed produces accurate free energies in cases where the common weighted-histogram analysis method (WHAM) for umbrella sampling fails because of slow dynamics within the windows. Even in the limit of completely uncorrelated data, where WHAM is optimal in the maximum-likelihood sense, DHAMed results are nearly indistinguishable. We illustrate DHAMed with applications to ion channel conduction, RNA duplex formation, α-helix folding, and rate calculations from accelerated molecular dynamics. DHAMed can also be used to construct Markov state models from biased or replica-exchange molecular dynamics simulations. By using binless WHAM formulated as a numerical minimization problem, the bias factors for the individual states can be determined efficiently in a preprocessing step and, if needed, optimized globally afterward.

Analytical transition-matrix treatment of electric multipole polarizabilities of hydrogen-like atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kharchenko, V.F., E-mail: vkharchenko@bitp.kiev.ua

2015-04-15

The direct transition-matrix approach to the description of the electric polarization of the quantum bound system of particles is used to determine the electric multipole polarizabilities of the hydrogen-like atoms. It is shown that in the case of the bound system formed by the Coulomb interaction the corresponding inhomogeneous integral equation determining an off-shell scattering function, which consistently describes virtual multiple scattering, can be solved exactly analytically for all electric multipole polarizabilities. Our method allows to reproduce the known Dalgarno–Lewis formula for electric multipole polarizabilities of the hydrogen atom in the ground state and can also be applied to determinemore » the polarizability of the atom in excited bound states. - Highlights: • A new description for electric polarization of hydrogen-like atoms. • Expression for multipole polarizabilities in terms of off-shell scattering functions. • Derivation of integral equation determining the off-shell scattering function. • Rigorous analytic solving the integral equations both for ground and excited states. • Study of contributions of virtual multiple scattering to electric polarizabilities.« less

75 FR 67019 - Presidential Determination on Major Illicit Drug Transit or Major Illicit Drug Producing...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-01

... base, and crack cocaine, primarily from Bolivia; and marijuana. The United States recognizes Brazil's... high- potency marijuana that is trafficked to the United States. The frequent mixing of methamphetamine... and synthetic drugs including marijuana, MDMA, and methamphetamine are produced in Canada and...

3 CFR - Presidential Determination on Major Illicit Drug Transit or Major Illicit Drug Producing...

Code of Federal Regulations, 2011 CFR

2011-01-01

... marijuana. The United States recognizes Brazil's emergence as a forward-leaning regional leader for... high-potency marijuana that is trafficked to the United States. The frequent mixing of methamphetamine... and synthetic drugs including marijuana, MDMA, and methamphetamine are produced in Canada and...

Critical behavior at a dynamic vortex insulator-to-metal transition

DOE PAGES

Poccia, Nicola; Baturina, Tatyana I.; Coneri, Francesco; ...

2015-09-10

An array of superconducting islands placed on a normal metal film offers a tunable realization of nanopatterned superconductivity. This system enables elucidating open questions concerning the nature of competing vortex states and phase transitions between them. A square array creates the egg crate potential in which magnetic field-induced vortices are frozen into a vortex insulator. We observe a vortex insulator-to-vortex metal transition driven by the applied electric current and determine critical exponents strikingly coinciding with those for thermodynamic liquid-gas transition. Lastly, our findings offer a comprehensive description of dynamic critical behavior and establish a deep connection between equilibrium and nonequilibriummore » phase transitions.« less

Critical behavior at a dynamic vortex insulator-to-metal transition.

PubMed

Poccia, Nicola; Baturina, Tatyana I; Coneri, Francesco; Molenaar, Cor G; Wang, X Renshaw; Bianconi, Ginestra; Brinkman, Alexander; Hilgenkamp, Hans; Golubov, Alexander A; Vinokur, Valerii M

2015-09-11

An array of superconducting islands placed on a normal metal film offers a tunable realization of nanopatterned superconductivity. This system enables investigation of the nature of competing vortex states and phase transitions between them. A square array creates the eggcrate potential in which magnetic field-induced vortices are frozen into a vortex insulator. We observed a vortex insulator-vortex metal transition driven by the applied electric current and determined critical exponents that coincided with those for thermodynamic liquid-gas transition. Our findings offer a comprehensive description of dynamic critical behavior and establish a deep connection between equilibrium and nonequilibrium phase transitions. Copyright © 2015, American Association for the Advancement of Science.

Numerical study of the effects of surface topography and chemistry on the wetting transition using the string method.

PubMed

Zhang, Yanan; Ren, Weiqing

2014-12-28

Droplets on a solid surface patterned with microstructures can exhibit the composite Cassie-Baxter (CB) state or the wetted Wenzel state. The stability of the CB state is determined by the energy barrier separating it from the wetted state. In this work, we study the CB to Wenzel transition using the string method [E et al., J. Chem. Phys. 126, 164103 (2007); W. Ren and E. Vanden-Eijnden, J. Chem. Phys. 138, 134105 (2013)]. We compute the transition states and energy barriers for a three-dimensional droplet on patterned surfaces. The liquid-vapor coexistence is modeled using the mean field theory. Numerical results are obtained for surfaces patterned with straight pillars and nails, respectively. It is found that on both type of surfaces, wetting occurs via infiltration of the liquid in a single groove. The reentrant geometry of nails creates large energy barrier for the wetting of the solid surface compared to straight pillars. We also study the effect of surface chemistry, pillar height, and inter-pillar spacing on the energy barrier and compare it with nails.

Numerical study of the effects of surface topography and chemistry on the wetting transition using the string method

NASA Astrophysics Data System (ADS)

Zhang, Yanan; Ren, Weiqing

2014-12-01

Droplets on a solid surface patterned with microstructures can exhibit the composite Cassie-Baxter (CB) state or the wetted Wenzel state. The stability of the CB state is determined by the energy barrier separating it from the wetted state. In this work, we study the CB to Wenzel transition using the string method [E et al., J. Chem. Phys. 126, 164103 (2007); W. Ren and E. Vanden-Eijnden, J. Chem. Phys. 138, 134105 (2013)]. We compute the transition states and energy barriers for a three-dimensional droplet on patterned surfaces. The liquid-vapor coexistence is modeled using the mean field theory. Numerical results are obtained for surfaces patterned with straight pillars and nails, respectively. It is found that on both type of surfaces, wetting occurs via infiltration of the liquid in a single groove. The reentrant geometry of nails creates large energy barrier for the wetting of the solid surface compared to straight pillars. We also study the effect of surface chemistry, pillar height, and inter-pillar spacing on the energy barrier and compare it with nails.

MgH Rydberg series: Transition energies from electron propagator theory and oscillator strengths from the molecular quantum defect orbital method

NASA Astrophysics Data System (ADS)

Corzo, H. H.; Velasco, A. M.; Lavín, C.; Ortiz, J. V.

2018-02-01

Vertical excitation energies belonging to several Rydberg series of MgH have been inferred from 3+ electron-propagator calculations of the electron affinities of MgH+ and are in close agreement with experiment. Many electronically excited states with n > 3 are reported for the first time and new insight is given on the assignment of several Rydberg series. Valence and Rydberg excited states of MgH are distinguished respectively by high and low pole strengths corresponding to Dyson orbitals of electron attachment to the cation. By applying the Molecular Quantum Defect Orbital method, oscillator strengths for electronic transitions involving Rydberg states also have been determined.

Improved transition path sampling methods for simulation of rare events

NASA Astrophysics Data System (ADS)

Chopra, Manan; Malshe, Rohit; Reddy, Allam S.; de Pablo, J. J.

2008-04-01

The free energy surfaces of a wide variety of systems encountered in physics, chemistry, and biology are characterized by the existence of deep minima separated by numerous barriers. One of the central aims of recent research in computational chemistry and physics has been to determine how transitions occur between deep local minima on rugged free energy landscapes, and transition path sampling (TPS) Monte-Carlo methods have emerged as an effective means for numerical investigation of such transitions. Many of the shortcomings of TPS-like approaches generally stem from their high computational demands. Two new algorithms are presented in this work that improve the efficiency of TPS simulations. The first algorithm uses biased shooting moves to render the sampling of reactive trajectories more efficient. The second algorithm is shown to substantially improve the accuracy of the transition state ensemble by introducing a subset of local transition path simulations in the transition state. The system considered in this work consists of a two-dimensional rough energy surface that is representative of numerous systems encountered in applications. When taken together, these algorithms provide gains in efficiency of over two orders of magnitude when compared to traditional TPS simulations.

MRCI study on the spectroscopic parameters, transition dipole moments and transition probabilities of 16 low-lying states of the BeB radical

NASA Astrophysics Data System (ADS)

Zhou, Dan; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue

2018-03-01

In this work, we calculate the potential energy curves of 16 Λ-S and 36 Ω states of beryllium boride (BeB) radical using the complete active space self-consistent field method, followed by the valence internally contracted multireference configuration interaction approach with Davidson correction. The 16 Λ-S states are the X2Π, A2Σ+, B2Π, C2Δ, D2Ʃ-, E2Σ+, G2Π, I2Σ+, a4Σ-, b4Π, c4Σ-, d4Δ, e4Σ+, g4Π, h4Π, and 24Σ+, which are obtained from the first three dissociation channels of the BeB radical. The Ω states are obtained from the Λ-S states. Of the Λ-S states, the G2Π, I2Σ+, and h4Π states exhibit double well curves. The G2Π, b4Π, and g4Π states are inverted with the spin-orbit coupling effect included. The d4Δ, e4Σ+, and g4Π states as well as the second well of the h4Π state are very weakly bound. Avoided crossings exist between the G2Π and H2Π states, the A2Σ+ and E2Σ+ states, the c4Σ- and f4Σ- states, the g4Π and h4Π states, the I2Σ+ and 42Σ+ states, as well as the 24Σ+ and 34Σ+ states. To improve the quality of the potential energy curves, core-valence correlation and scalar relativistic corrections, as well as the extrapolation of the potential energies to the complete basis set limit, are included. The transition dipole moments are computed. Spectroscopic parameters and vibrational levels are determined along with Franck-Condon factors, Einstein coefficients, and radiative lifetimes of many electronic transitions. The transition probabilities are evaluated. The spin-orbit coupling effect on the spectroscopic parameters and vibrational levels is discussed. The spectroscopic parameters, vibrational levels, and transition probabilities reported in this paper can be considered very reliable and can be employed to predict these states in an appropriate spectroscopy experiment.

Brillouin-scattering study of liquid-glass transitions in ternary mixtures of water, trehalose, and an ionic liquid

NASA Astrophysics Data System (ADS)

Takayama, Haruki; Shibata, Tomohiko; Ishii, Takahiro; Kojima, Seiji

2013-04-01

Ternary mixtures of water, sugar, and ionic liquid have been studied as new candidates for bioprotectants. To clarify the elastic properties and relaxation dynamics of the supercooled liquid and glassy states at low temperatures, the liquid-glass transitions were investigated by using a micro-Brillouin-scattering technique. The refractive index was measured accurately as a function of content and temperature to determine the sound velocity and the attenuation from Brillouin frequency shift and peak width. The relaxation times of structural relaxations related to liquidglass transitions were determined as functions of temperature. The Meyer-Neldel rule was found to hold for the activation energy and the prefactor of the Arrhenius law for the relaxation time.

Heterogeneous to homogeneous melting transition visualized with ultrafast electron diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

The ultrafast laser excitation of matters leads to non-equilibrium states with complex solid-liquid phase transition dynamics. We used electron diffraction at mega-electronvolt energies to visualize the ultrafast melting of gold on the atomic scale length. For energy densities approaching the irreversible melting regime, we first observed heterogeneous melting on time scales of 100 ps to 1000 ps, transitioning to homogeneous melting that occurs catastrophically within 10-20 ps at higher energy densities. We showed evidence for the heterogeneous coexistence of solid and liquid. We determined the ion and electron temperature evolution and found superheated conditions. Our results constrain the electron-ion couplingmore » rate, determine the Debye temperature and reveal the melting sensitivity to nucleation seeds.« less

Dynamical predictors of an imminent phenotypic switch in bacteria

NASA Astrophysics Data System (ADS)

Wang, Huijing; Ray, J. Christian J.

2017-08-01

Single cells can stochastically switch across thresholds imposed by regulatory networks. Such thresholds can act as a tipping point, drastically changing global phenotypic states. In ecology and economics, imminent transitions across such tipping points can be predicted using dynamical early warning indicators. A typical example is ‘flickering’ of a fast variable, predicting a longer-lasting switch from a low to a high state or vice versa. Considering the different timescales between metabolite and protein fluctuations in bacteria, we hypothesized that metabolic early warning indicators predict imminent transitions across a network threshold caused by enzyme saturation. We used stochastic simulations to determine if flickering predicts phenotypic transitions, accounting for a variety of molecular physiological parameters, including enzyme affinity, burstiness of enzyme gene expression, homeostatic feedback, and rates of metabolic precursor influx. In most cases, we found that metabolic flickering rates are robustly peaked near the enzyme saturation threshold. The degree of fluctuation was amplified by product inhibition of the enzyme. We conclude that sensitivity to flickering in fast variables may be a possible natural or synthetic strategy to prepare physiological states for an imminent transition.

Nuclear Structure of the Closed Subshell Nucleus 90Zr Studied with the (n,n'(gamma)) Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garrett, P E; Younes, Y; Becker, J A

States in {sup 90}Zr have been observed with the (n,n{prime}{gamma}) reaction using both spallation and monoenergetic accelerator-produced neutrons. A scheme comprised of 81 levels and 157 transitions was constructed concentrating on levels below 5.6 MeV in excitation energy. Spins have been determined by considering data from all experimental studies performed for {sup 90}Zr. Lifetimes have been deduced using the Doppler-shift attenuation method for many of the states and transition rates have been obtained. A spherical shell-model interpretation in terms of particle-hole excitations assuming a {sup 88}Sr closed core is given. In some cases, enhancements in B(M1) and B(E2) values aremore » observed that cannot be explained by assuming simple particle-hole excitations. Shell-model calculations using an extended f pg-shell model space reproduce the spectrum of excited states very well, and the gross features of the B(M1) and B(E2) transition rates. Transition rates for individual levels show discrepancies between calculations and experimental values.« less

The Transition from Single-Sex to Coeducational High Schools: Effects on Multiple Dimensions of Self-Concept and on Academic Achievement.

ERIC Educational Resources Information Center

Marsh, Herbert W.; And Others

1988-01-01

Self-concept measures and state certificate program achievement grades were used to determine the effects on 7th through 11th graders in Sydney (Australia) of converting two single-sex high schools to coeducational institutions. Pre- to post-transition data were collected from 1982 to 1985. Coeducational organizations benefit self-concept, while…

Force transients and minimum cross-bridge models in muscular contraction

PubMed Central

Halvorson, Herbert R.

2010-01-01

Two- and three-state cross-bridge models are considered and examined with respect to their ability to predict three distinct phases of the force transients that occur in response to step change in muscle fiber length. Particular attention is paid to satisfying the Le Châtelier–Brown Principle. This analysis shows that the two-state model can account for phases 1 and 2 of a force transient, but is barely adequate to account for phase 3 (delayed force) unless a stretch results in a sudden increase in the number of cross-bridges in the detached state. The three-state model (A → B → C → A) makes it possible to account for all three phases if we assume that the A → B transition is fast (corresponding to phase 2), the B → C transition is of intermediate speed (corresponding to phase 3), and the C → A transition is slow; in such a scenario, states A and C can support or generate force (high force states) but state B cannot (detached, or low-force state). This model involves at least one ratchet mechanism. In this model, force can be generated by either of two transitions: B → A or B → C. To determine which of these is the major force-generating step that consumes ATP and transduces energy, we examine the effects of ATP, ADP, and phosphate (Pi) on force transients. In doing so, we demonstrate that the fast transition (phase 2) is associated with the nucleotide-binding step, and that the intermediate-speed transition (phase 3) is associated with the Pi-release step. To account for all the effects of ligands, it is necessary to expand the three-state model into a six-state model that includes three ligand-bound states. The slowest phase of a force transient (phase 4) cannot be explained by any of the models described unless an additional mechanism is introduced. Here we suggest a role of series compliance to account for this phase, and propose a model that correlates the slowest step of the cross-bridge cycle (transition C → A) to: phase 4 of step analysis, the rate constant ktr of the quick-release and restretch experiment, and the rate constant kact for force development time course following Ca2+ activation. PMID:18425593

Force transients and minimum cross-bridge models in muscular contraction.

PubMed

Kawai, Masataka; Halvorson, Herbert R

2007-01-01

Two- and three-state cross-bridge models are considered and examined with respect to their ability to predict three distinct phases of the force transients that occur in response to step change in muscle fiber length. Particular attention is paid to satisfying the Le Châtelier-Brown Principle. This analysis shows that the two-state model can account for phases 1 and 2 of a force transient, but is barely adequate to account for phase 3 (delayed force) unless a stretch results in a sudden increase in the number of cross-bridges in the detached state. The three-state model (A-->B-->C-->A) makes it possible to account for all three phases if we assume that the A-->B transition is fast (corresponding to phase 2), the B-->A transition is of intermediate speed (corresponding to phase 3), and the C-->A transition is slow; in such a scenario, states A and C can support or generate force (high force states) but state B cannot (detached, or low-force state). This model involves at least one ratchet mechanism. In this model, force can be generated by either of two transitions: B-->A or B-->C. To determine which of these is the major force-generating step that consumes ATP and transduces energy, we examine the effects of ATP, ADP, and phosphate (Pi) on force transients. In doing so, we demonstrate that the fast transition (phase 2) is associated with the nucleotide-binding step, and that the intermediate-speed transition (phase 3) is associated with the Pi-release step. To account for all the effects of ligands, it is necessary to expand the three-state model into a six-state model that includes three ligand-bound states. The slowest phase of a force transient (phase 4) cannot be explained by any of the models described unless an additional mechanism is introduced. Here we suggest a role of series compliance to account for this phase, and propose a model that correlates the slowest step of the cross-bridge cycle (transition C-->A) to: phase 4 of step analysis, the rate constant k(tr) of the quick-release and restretch experiment, and the rate constant k(act) for force development time course following Ca(2+) activation.

High Pressure ZZ-Exchange NMR Reveals Key Features of Protein Folding Transition States.

PubMed

Zhang, Yi; Kitazawa, Soichiro; Peran, Ivan; Stenzoski, Natalie; McCallum, Scott A; Raleigh, Daniel P; Royer, Catherine A

2016-11-23

Understanding protein folding mechanisms and their sequence dependence requires the determination of residue-specific apparent kinetic rate constants for the folding and unfolding reactions. Conventional two-dimensional NMR, such as HSQC experiments, can provide residue-specific information for proteins. However, folding is generally too fast for such experiments. ZZ-exchange NMR spectroscopy allows determination of folding and unfolding rates on much faster time scales, yet even this regime is not fast enough for many protein folding reactions. The application of high hydrostatic pressure slows folding by orders of magnitude due to positive activation volumes for the folding reaction. We combined high pressure perturbation with ZZ-exchange spectroscopy on two autonomously folding protein domains derived from the ribosomal protein, L9. We obtained residue-specific apparent rates at 2500 bar for the N-terminal domain of L9 (NTL9), and rates at atmospheric pressure for a mutant of the C-terminal domain (CTL9) from pressure dependent ZZ-exchange measurements. Our results revealed that NTL9 folding is almost perfectly two-state, while small deviations from two-state behavior were observed for CTL9. Both domains exhibited large positive activation volumes for folding. The volumetric properties of these domains reveal that their transition states contain most of the internal solvent excluded voids that are found in the hydrophobic cores of the respective native states. These results demonstrate that by coupling it with high pressure, ZZ-exchange can be extended to investigate a large number of protein conformational transitions.

Two-step photoconductivity in LiY x Lu1 - x F4:Ce,Yb crystals

NASA Astrophysics Data System (ADS)

Nurtdinova, L. A.; Korableva, S. L.; Leontiev, A. V.

2016-10-01

Photoconductivity of LiY x Lu1- x F4:Ce,Yb ( x = 0-1) crystals is measured under one- and two-step excitation. It is established that the photoconductivity is due to intra-center transitions from excited states of Ce3+ ions. The position of the ground 4 f-state of Ce3+ ion relative to the bottom of the conduction band is determined. The choice of pumping conditions to obtain the lasing on the 5 d-4 f transitions of trivalent cerium in these active media is substantiated.

On entropy determination from magnetic and calorimetric experiments in conventional giant magnetocaloric materials

NASA Astrophysics Data System (ADS)

Chen, Jing-Han; Us Saleheen, Ahmad; Adams, Philip W.; Young, David P.; Ali, Naushad; Stadler, Shane

2018-04-01

In this work, we discuss measurement protocols for the determination of the magnetic entropy change associated with first-order magneto-structural transitions from both magnetization and calorimetric experiments. The Cu-doped Ni2MnGa Heusler alloy with a first-order magneto-structural phase transition is used as a case study to illustrate how commonly-used magnetization measurement protocols result in spurious entropy evaluations. Two magnetization measurement protocols which allow for the accurate assessment of the magnetic entropy change across first-order magneto-structural transitions are presented. In addition, calorimetric measurements were performed to validate the results from the magnetization measurements. Self-consistent results between the magnetization and calorimetric measurements were obtained when the non-equilibrium thermodynamic state was carefully handled. Such methods could be applicable to other systems displaying giant magnetocaloric effects caused by first-order phase transitions with magnetic and thermal hysteresis.

Detecting critical state before phase transition of complex systems by hidden Markov model

NASA Astrophysics Data System (ADS)

Liu, Rui; Chen, Pei; Li, Yongjun; Chen, Luonan

Identifying the critical state or pre-transition state just before the occurrence of a phase transition is a challenging task, because the state of the system may show little apparent change before this critical transition during the gradual parameter variations. Such dynamics of phase transition is generally composed of three stages, i.e., before-transition state, pre-transition state, and after-transition state, which can be considered as three different Markov processes. Thus, based on this dynamical feature, we present a novel computational method, i.e., hidden Markov model (HMM), to detect the switching point of the two Markov processes from the before-transition state (a stationary Markov process) to the pre-transition state (a time-varying Markov process), thereby identifying the pre-transition state or early-warning signals of the phase transition. To validate the effectiveness, we apply this method to detect the signals of the imminent phase transitions of complex systems based on the simulated datasets, and further identify the pre-transition states as well as their critical modules for three real datasets, i.e., the acute lung injury triggered by phosgene inhalation, MCF-7 human breast cancer caused by heregulin, and HCV-induced dysplasia and hepatocellular carcinoma.

A multi-state model examining patterns of transitioning among states of engagement in care in HIV-positive individuals initiating combination antiretroviral therapy

PubMed Central

Gillis, Jennifer; Loutfy, Mona; Bayoumi, Ahmed M; Antoniou, Tony; Burchell, Ann N; Walmsley, Sharon; Cooper, Curtis; Klein, Marina B.; Machouf, Nima; Montaner, Julio SG; Rourke, Sean B.; Tsoukas, Christos; Hogg, Robert; Raboud, Janet

2016-01-01

Background Common measures of engagement in care fail to acknowledge that infrequent follow-up may occur either intentionally among patients with sustained virologic suppression or unintentionally among patients with poor clinical outcomes. Methods Five states of HIV care were defined within the Canadian Observational Cohort (CANOC) Collaboration following combination antiretroviral therapy (cART) initiation: (1) guidelines HIV care (suppressed viral load (VL) and CD4 >200 cells/mm3, no gaps in cART >3 months, no gaps in CD4 or VL measurement >6 months), (2) successful care with decreased frequency of follow-up (as above except no gaps in CD4 or VL measurement >12 months), (3) suboptimal care (unsuppressed VL, CD4<200 cells/mm3 on 2 consecutive visits, ≥1 gap in cART >3 months, or ≥1 gap in CD4 or VL measurement >12 months), (4) loss to follow-up (no contact for 18 months), and (5) death. Multi-state models were used to determine factors associated with transitioning among states. Results 7810 participants were included. Younger age, female gender, Indigenous ethnicity and people who have injected drugs (PWID) were associated with increased likelihoods of transitioning from guidelines to suboptimal care and decreased likelihoods of transitioning from suboptimal to guidelines care. One-fifth of individuals in successful, decreased follow-up after cART initiation (mean sojourn time 0.72 years) were in suboptimal care in subsequent years. Conclusions Using routinely collected data, we have developed a flexible framework that characterizes patient transitions among states of HIV clinical care. We have demonstrated that multi-state models provide a useful approach to supplement ‘cascade of care’ work. PMID:27851713

Electron impact excitation of the electronic states of N2. III - Transitions in the 12.5-14.2-eV energy-loss region at incident energies of 40 and 60 eV

NASA Technical Reports Server (NTRS)

Chutjian, A.; Trajmar, S.; Cartwright, D. C.

1977-01-01

Analysis of electron energy-loss data at incident electron energies of 40 and 60 eV has led to the determination of normalized absolute differential cross sections for electron-impact excitation of five optically-allowed singlet states, two known triplet states, and two unknown triplet-like states of N2, lying in the energy-loss range 12.5-14.2 eV. The range of scattering angles was 5 to 138 deg. The optically allowed transitions and the known triplet excitations are identified. Cross sections for excitation to two unidentified triplet-like states at 13.155 and 13.395 eV were also obtained. The relationship of the generalized oscillator strength for the dipole-allowed states obtained from the described data to known optical oscillator strengths is discussed.

The Rotational Spectrum of Iodine Dioxide, OIO

NASA Technical Reports Server (NTRS)

Miller, Charles E.; Cohen, Edward A.

2000-01-01

The rotational spectra of OIO in its ground vibrational and first excited bending states have been observed for the first time. OIO was formed initially from the products of a microwave discharge in O2 passing over molecular iodine and later with greater yield in a DC discharge through a mixture of O2 and I2 vapor. OIO is an asymmetric prolate rotor (kappa = -0.690) with a (sup 2)B(sub 1) electronic ground state. Over 550 ground state transitions and over 160 transitions of the excited bending state have been included in the fits. The resulting parameters are well determined and will be compared to those recently published for OBrO and OClO. These will be interpreted in terms of the molecular geometry, harmonic force field, and electronic structure.

Mechanics of Boundary Layer Transition. Part 5: Boundary Layer Stability theory in incompressible and compressible flow

NASA Technical Reports Server (NTRS)

Mack, L. M.

1967-01-01

The fundamentals of stability theory, its chief results, and the physical mechanisms at work are presented. The stability theory of the laminar boundary determines whether a small disturbance introduced into the boundary layer will amplify or damp. If the disturbance damps, the boundary layer remains laminar. If the disturbance amplifies, and by a sufficient amount, then transition to turbulence eventually takes place. The stability theory establishes those states of the boundary layer which are most likely to lead to transition, identifys those frequencies which are the most dangerous, and indicates how the external parameters can best be changed to avoid transition.

Optogalvanic spectroscopy of lanthanum hyperfine structure

NASA Astrophysics Data System (ADS)

Nelson, Amanda; Hankes, Jessie; Banner, Patrick; Olmschenk, Steven

2017-04-01

Optogalvanic spectroscopy is a sensitive technique to measure optical transitions of atoms and ions produced in a high voltage discharge. Advantages of this technique include a comparatively simple optical setup and the ability to interrogate excited state transitions. Here, we use optogalavanic spectroscopy in a hollow cathode lamp to measure the hyperfine spectrum of several transitions in lanthanum. Hyperfine coefficients are determined for the corresponding energy levels and compared to available previous measurements. This research is supported by the Army Research Office, Research Corporation for Science Advancement, and Denison University.

Evidence for a first-order liquid-liquid transition in high-pressure hydrogen from ab initio simulations

PubMed Central

Morales, Miguel A.; Pierleoni, Carlo; Schwegler, Eric; Ceperley, D. M.

2010-01-01

Using quantum simulation techniques based on either density functional theory or quantum Monte Carlo, we find clear evidence of a first-order transition in liquid hydrogen, between a low conductivity molecular state and a high conductivity atomic state. Using the temperature dependence of the discontinuity in the electronic conductivity, we estimate the critical point of the transition at temperatures near 2,000 K and pressures near 120 GPa. Furthermore, we have determined the melting curve of molecular hydrogen up to pressures of 200 GPa, finding a reentrant melting line. The melting line crosses the metalization line at 700 K and 220 GPa using density functional energetics and at 550 K and 290 GPa using quantum Monte Carlo energetics. PMID:20566888

A Networks Approach to Modeling Enzymatic Reactions.

PubMed

Imhof, P

2016-01-01

Modeling enzymatic reactions is a demanding task due to the complexity of the system, the many degrees of freedom involved and the complex, chemical, and conformational transitions associated with the reaction. Consequently, enzymatic reactions are not determined by precisely one reaction pathway. Hence, it is beneficial to obtain a comprehensive picture of possible reaction paths and competing mechanisms. By combining individually generated intermediate states and chemical transition steps a network of such pathways can be constructed. Transition networks are a discretized representation of a potential energy landscape consisting of a multitude of reaction pathways connecting the end states of the reaction. The graph structure of the network allows an easy identification of the energetically most favorable pathways as well as a number of alternative routes. © 2016 Elsevier Inc. All rights reserved.

Relativistic many-body calculation of energies, multipole transition rates, and lifetimes in tungsten ions

NASA Astrophysics Data System (ADS)

Safronova, U. I.; Safronova, M. S.; Nakamura, N.

2017-04-01

Atomic properties of Cd-like W26 +, In-like W25 +, and Sn-like W24 + ions are evaluated by using a relativistic CI+all -order approach that combines configuration-interaction and the coupled-cluster methods. The energies, transition rates, and lifetimes of low-lying levels are calculated and compared with available theoretical and experimental values. The magnetic-dipole transition rates are calculated to determine the branching ratios and lifetimes for the 4 f3 states in W25 + and for the 4 f4 states in W24 + ions. Excellent agreement of the CI+all -order values provided a benchmark test of this method for the 4 fn configurations validating the recommended values of tungsten ion properties calculated in this work.

Fatal attraction in glycolysis: how Saccharomyces cerevisiae manages sudden transitions to high glucose

PubMed Central

Heerden, Johan H. v.; Wortel, Meike T.; Bruggeman, Frank J.; Heijnen, Joseph J.; Bollen, Yves J.; Planqué, Robert; Hulshof, Josephus; O’Toole, Tom G.; Wahl, S. A.; Teusink, Bas

2014-01-01

In the model eukaryote Saccharomyces cerevisiae, it has long been known that a functional trehalose pathway is indispensable for transitions to high glucose conditions. Upon addition of glucose, cells with a defect in trehalose 6-phosphate synthase (Tps1), the first committed step in the trehalose pathway, display what we have termed an imbalanced glycolytic state; in this state the flux through the upper part of glycolysis outpaces that through the lower part of glycolysis. As a consequence, the intermediate fructose 1,6-bisphosphate (FBP) accumulates at low concentrations of ATP and inorganic phosphate (Pi). Despite significant research efforts, a satisfactory understanding of the regulatory role that trehalose metabolism plays during such transitions has remained infamously unresolved. In a recent study, we demonstrate that the startup of glycolysis exhibits two dynamic fates: a proper, functional, steady state or the imbalanced state described above. Both states are stable, attracting states, and the probability distribution of initial states determines the fate of a yeast cell exposed to glucose. Trehalose metabolism steers the dynamics of glycolysis towards the proper functional state through its ATP hydrolysis activity; a mechanism that ensures that the demand and supply of ATP is balanced with Pi availability under dynamic conditions. [van Heerden et al. Science (2014), DOI: 10.1126/science.1245114.] PMID:28357229

Spectroscopy of Vibrational States in Diatomic Iodine Molecules

NASA Astrophysics Data System (ADS)

Mulholland, Mary; Harrill, Charles H.; Smith, R. Seth

2015-04-01

This project is focused on understanding the vibrational structure of iodine, which is a homonuclear diatomic molecule. A 20 mW, 532 nm cw diode laser was used to selectively excite neutral iodine molecules to a higher energy electronic state. By performing spectroscopy on the transitions from this state to a lower energy electronic state, the data only showed those vibrational bands which connect the two electronic states. Since a number of vibrational levels are populated in the higher energy electronic state, the transitions to all of the allowed vibrational levels in the lower energy electronic state provided sufficient data to determine the vibrational structures of both states. Emission spectra were collected with an Ocean Optics USB4000 Compact CCD Spectrometer. The spectrometer had a range of 500 - 770 nm with a resolution of approximately 0.5 nm and was sensitive enough to resolve the vibrational states in diatomic iodine molecules. The results were compared to a simple harmonic oscillator model.

Kinetic isotope effects reveal early transition state of protein lysine methyltransferase SET8

PubMed Central

Linscott, Joshua A.; Kapilashrami, Kanishk; Wang, Zhen; Senevirathne, Chamara; Bothwell, Ian R.; Blum, Gil; Luo, Minkui

2016-01-01

Protein lysine methyltransferases (PKMTs) catalyze the methylation of protein substrates, and their dysregulation has been linked to many diseases, including cancer. Accumulated evidence suggests that the reaction path of PKMT-catalyzed methylation consists of the formation of a cofactor(cosubstrate)–PKMT–substrate complex, lysine deprotonation through dynamic water channels, and a nucleophilic substitution (SN2) transition state for transmethylation. However, the molecular characters of the proposed process remain to be elucidated experimentally. Here we developed a matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) method and corresponding mathematic matrix to determine precisely the ratios of isotopically methylated peptides. This approach may be generally applicable for examining the kinetic isotope effects (KIEs) of posttranslational modifying enzymes. Protein lysine methyltransferase SET8 is the sole PKMT to monomethylate histone 4 lysine 20 (H4K20) and its function has been implicated in normal cell cycle progression and cancer metastasis. We therefore implemented the MS-based method to measure KIEs and binding isotope effects (BIEs) of the cofactor S-adenosyl-l-methionine (SAM) for SET8-catalyzed H4K20 monomethylation. A primary intrinsic 13C KIE of 1.04, an inverse intrinsic α-secondary CD3 KIE of 0.90, and a small but statistically significant inverse CD3 BIE of 0.96, in combination with computational modeling, revealed that SET8-catalyzed methylation proceeds through an early, asymmetrical SN2 transition state with the C-N and C-S distances of 2.35–2.40 Å and 2.00–2.05 Å, respectively. This transition state is further supported by the KIEs, BIEs, and steady-state kinetics with the SAM analog Se-adenosyl-l-selenomethionine (SeAM) as a cofactor surrogate. The distinct transition states between protein methyltransferases present the opportunity to design selective transition-state analog inhibitors. PMID:27940912

Dynamic heterogeneity in the folding/unfolding transitions of FiP35

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mori, Toshifumi, E-mail: mori@ims.ac.jp; Saito, Shinji, E-mail: shinji@ims.ac.jp

Molecular dynamics simulations have become an important tool in studying protein dynamics over the last few decades. Atomistic simulations on the order of micro- to milliseconds are becoming feasible and are used to study the state-of-the-art experiments in atomistic detail. Yet, analyzing the high-dimensional-long-temporal trajectory data is still a challenging task and sometimes leads to contradictory results depending on the analyses. To reveal the dynamic aspect of the trajectory, here we propose a simple approach which uses a time correlation function matrix and apply to the folding/unfolding trajectory of FiP35 WW domain [Shaw et al., Science 330, 341 (2010)]. Themore » approach successfully characterizes the slowest mode corresponding to the folding/unfolding transitions and determines the free energy barrier indicating that FiP35 is not an incipient downhill folder. The transition dynamics analysis further reveals that the folding/unfolding transition is highly heterogeneous, e.g., the transition path time varies by ∼100 fold. We identify two misfolded states and show that the dynamic heterogeneity in the folding/unfolding transitions originates from the trajectory being trapped in the misfolded and half-folded intermediate states rather than the diffusion driven by a thermal noise. The current results help reconcile the conflicting interpretations of the folding mechanism and highlight the complexity in the folding dynamics. This further motivates the need to understand the transition dynamics beyond a simple free energy picture using simulations and single-molecule experiments.« less

Transition and duration in disability: New evidence from administrative data.

PubMed

Lopez Casasnovas, Guillem; Nicodemo, Catia

2016-01-01

In recent decades demographic changes (low fertility rates, increased life expectancy…) in most OECD countries, have brought profound changes in the population pyramid, with several effects in the welfare of society. One of them is the increase in the number of people with disabilities, since age is a determining factor in the emergence of this dependency. This paper studies the probability to enter and transit in and from a disability state, as well as its associated mortality, by attending to the distinction between the initial disability level and the process that leads on from it, and by addressing whether and how education, age and income affect this transition. Applying a Markov model and a survival analysis to new Spanish administrative data set (Muestra Continua de Vida Laboral (MCVL)) we estimate the probability that a person changes the state of disability and the duration of her progression in each case. We find that people with an initial state of disability have a higher propensity to change status and take less time to transit amongst different stages than those who have no disability. Men do so more frequently than women and income have negative effects on the transition. These results may help to incorporate into welfare programs some protection mechanisms for delaying transitions and target the most fragile population groups. Copyright © 2016 Elsevier Inc. All rights reserved.

RURAL EDUCATION IN TRANSITION, A STUDY OF TRENDS AND PATTERNS IN LOUISIANA.

ERIC Educational Resources Information Center

BERTRAND, ALVIN L.; SMITH, MARION B.

POPULATION TRENDS, DEFINED AS DISTRIBUTION, COMPOSITION, AND CHANGES IN NUMBERS WERE DETERMINED IN THIS DOCUMENT FOR THE STATE OF LOUISIANA. DATA WERE GATHERED FROM PUBLICATIONS OF THE BUREAU OF THE CENSUS, THE LOUISIANA STATE DEPARTMENT OF EDUCATION, AND QUESTIONNAIRE RESPONSES OF HIGH SCHOOL JUNIORS AND SENIORS IN SELECTED SAMPLE SCHOOLS. THE…

Infrared absorption and admittance spectroscopy of Ge quantum dots on a strained SiGe layer

NASA Astrophysics Data System (ADS)

Yakimov, A. I.; Nikiforov, A. I.; Timofeev, V. A.; Dvurechenskii, A. V.

2011-12-01

A combined infrared absorption and admittance spectroscopy is carried out in examining the energy level structure and the hole emission process in self-assembled Ge quantum dots (QDs) placed on a strained Si0.65Ge0.35 quantum well (QW), which, in turn, is incorporated in a Si matrix. In the midinfrared spectral range, the dots exhibit three dominant absorption bands peaked at 130, 250 and 390 meV. By a comparison between absorption measurements and six-band {\\bf k}\\;{\\bm \\cdot}\\;{\\bf p} calculations, the long-wave (~130 meV) resonance is attributed to a transition from the QD hole ground state to the two-dimensional heavy-hole states confined in the Si0.65Ge0.35 layer. The mid-wave absorption band around 390 meV is ascribed to a transition from the QD hole ground state to the three-dimensional continuum states of the Si matrix. An equivalent absorption cross section for these two types of transitions is determined to be 1.2 × 10-15 cm2 and 1.2 × 10-16 cm2, respectively. The origin of the transmission minimum around 250 meV is more ambiguous. We tentatively propose that it can be due to transition either from the highest heavy-hole subband of the Si0.65Ge0.35 QW to continuum states above the Si barrier or from the dot states to the light-hole and split-off subbands of the Si0.65Ge0.35 layer. The photoinduced bleaching of the near-infrared absorption is detected under interband optical excitation of undoped samples. This finding is explained by blocking the interband transitions inside the dots due to the state filling effect. By using the admittance spectroscopy, the mechanism of hole escape from QDs in the presence of an ac vertical electric field is identified. A thermally activated emission from the QD ground state into the two-dimensional states of the Si0.65Ge0.35 well is observed. From the temperature- and frequency-dependent measurements the QD hole ground state is determined to be located ~160 meV below the heavy-hole subband of the Si0.65Ge0.35 layer in good agreement with the results obtained by infrared absorption spectroscopy and six-band {\\bf k}\\;{\\bm \\cdot}\\;{\\bf p} theory. The information acquired from our experimental observations is valuable for feasible device applications.

High-resolution rovibrational study of the Coriolis-coupled v 12 and v 15 modes of [1.1.1]propellane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirkpatrick, Robynne W; Masiello, Tony; Jariyasopit, Narumol

Infrared spectra of the small strained cage molecule [1.1.1]propellane have been obtained at high resolution (0.0015 cm -1) and the J and K, l rovibrational structure has been resolved for the first time. We recently used combination-differences to obtain ground state parameters for propellane; over 4,100 differences from five fundamental and four combination bands were used in this process. The combination-difference approach eliminated errors due to localized perturbations in the upper state levels of the transitions and gave well-determined ground state parameters. In the current work, these ground state parameters were used in a determination of the upper state parametersmore » for the v 12(e') perpendicular and v 15(a 2") parallel bands. Over 4000 infrared transitions were fitted for each band, with J, K values ranging up to 71, 51 and 92, 90 respectively. While the transition frequencies for both bands can be fit nicely using separate analyses for each band, the strong intensity perturbations observed in the weaker v 12 band indicated that Coriolis coupling between the two modes was significant and should be included. Due to correlations with other parameters, the Coriolis coupling parameter ζ y 15,12a for the v 15 and v 12 interaction is poorly determined by a transition frequency fit alone. However, by combining the frequency fit with a fit of experimental intensities, a value of -0.42 was obtained, quite close to that predicted from the ab initio calculation (-0.44). This intensity fit also yielded a (∂μ z/∂Q 15)/(∂μ x/∂Q 12a) dipole derivative ratio of 36.5, in reasonable agreement with a value of 29.2 predicted by Gaussian ab initio density functional calculations using a cc-pVTZ basis. This ratio is unusually high due to large charge movement as the novel central Caxial-Caxial bond is displaced along the symmetry axis of the molecule for the v 15 mode.« less

The Electronic-Vibrational Behaviour of O2 in the Upper Atmosphere under Night-time Auroral Conditions

NASA Astrophysics Data System (ADS)

Jones, D. B.; Cartwright, D. C.; Campbell, L.; Teubner, P. J. O.; Brunger, M. J.; Bottema, M. J.

2004-09-01

We report on the extension of our Statistical Equlibrium Code (SEC) to determine the electronic-vibrational behaviour of O2 in the thermosphere, under night-time auroral conditions. This work was necessitated by the inadequacies in previous studies where the electron-impact cross section data bases employed have been superceeded, and/or direct excitation of states via electron impact has been neglected. Here we use the latest electron-impact cross section data bases to present the first electron-impact excitation rates for the 8 lowest lying electronic states of O_2. We then use these rates in conjunction with the most accurately available Franck-Condon factors, transition probabilities and quenching rates to determine the excited state populations. Note that predissociation, which is important for O_2, is also included in our model. We present radiative rates for various transitions and compare these results with those from other models and experimental rocket measurements.

The special features of the crystal structure and properties of oxides with mixed conductivity based on lanthanum gallate

NASA Astrophysics Data System (ADS)

Politova, E. D.; Ivanov, S. A.; Kaleva, G. M.; Mosunov, A. V.; Rusakov, V. S.

2008-10-01

The paper presents a review of works on the synthesis, structural composition effects, phase transitions, and electrical conductivity properties of multicomponent solid solutions based on heterosubstituted lanthanum gallate (La,A)(Ga,M)O3 - y . High-temperature phase transitions and structural and charge ordering effects were studied. The presence of iron cations in different valence states was proved; the relative contents of these cations depended on the x parameter and nonstoichiometry parameter y of the base composition. For M = Fe, antiferromagnetic ordering was observed; its temperature interval was determined by the concentration of iron cations in the high-spin state. The total conductivity was found to increase as the concentration of transition metal cations grew because of an increase in the electronic conductivity component. The data on structural parameters and dc and ac conductivity substantiated the conclusion that the highest ionic conductivity and permeability to oxygen were characteristic of iron-containing oxides. The results obtained are evidence that crystal chemical factors play a determining role in the formation of the ion-conducting properties of anion-deficient perovskite-like oxides.

Transition probabilities in neutron-rich Se,8280 and the role of the ν g9 /2 orbital

NASA Astrophysics Data System (ADS)

Litzinger, J.; Blazhev, A.; Dewald, A.; Didierjean, F.; Duchêne, G.; Fransen, C.; Lozeva, R.; Verney, D.; de Angelis, G.; Bazzacco, D.; Birkenbach, B.; Bottoni, S.; Bracco, A.; Braunroth, T.; Cederwall, B.; Corradi, L.; Crespi, F. C. L.; Désesquelles, P.; Eberth, J.; Ellinger, E.; Farnea, E.; Fioretto, E.; Gernhäuser, R.; Goasduff, A.; Görgen, A.; Gottardo, A.; Grebosz, J.; Hackstein, M.; Hess, H.; Ibrahim, F.; Jolie, J.; Jungclaus, A.; Kolos, K.; Korten, W.; Leoni, S.; Lunardi, S.; Maj, A.; Menegazzo, R.; Mengoni, D.; Michelagnoli, C.; Mijatovic, T.; Million, B.; Möller, O.; Modamio, V.; Montagnoli, G.; Montanari, D.; Morales, A. I.; Napoli, D. R.; Niikura, M.; Pietralla, N.; Pollarolo, G.; Pullia, A.; Quintana, B.; Recchia, F.; Reiter, P.; Rosso, D.; Sahin, E.; Salsac, M. D.; Scarlassara, F.; Söderström, P.-A.; Stefanini, A. M.; Stezowski, O.; Szilner, S.; Theisen, Ch.; Valiente-Dobón, J. J.; Vandone, V.; Vogt, A.

2018-04-01

Transition probabilities of intermediate-spin yrast and non-yrast excitations in Se,8280 were investigated in a recoil distance Doppler-shift (RDDS) experiment performed at the Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Legnaro. The Cologne Plunger device for deep inelastic scattering was used for the RDDS technique and was combined with the AGATA Demonstrator array for the γ -ray detection and coupled to the PRISMA magnetic spectrometer for an event-by-event particle identification. In 80Se, the level lifetimes of the yrast (61+) and (81+) states and of a non-yrast band feeding the yrast 41+ state are determined. A spin and parity assignment of the head of this sideband is discussed based on the experimental results and supported by large-scale shell-model calculations. In 82Se, the level lifetimes of the yrast 61+ state and the yrare 42+ state and lifetime limits of the yrast (101+) state and of the 51- state are determined. Although the experimental results contain large uncertainties, they are interpreted with care in terms of large-scale shell-model calculations using the effective interactions JUN45 and jj44b. The excited states' wave functions are investigated and discussed with respect to the role of the neutron g9 /2 orbital.

The far-infrared laser magnetic resonance spectrum of the SiH radical and determination of ground state parameters

NASA Technical Reports Server (NTRS)

Brown, J. M.; Curl, R. F.; Evenson, K. M.

1984-01-01

The far-infrared laser magnetic resonance spectrum of the SiH radical in the v = O level of its X2Pi state has been recorded. The signals are rather weak. The molecules were generated in the reaction between fluorine atoms and SiH4. Rotational transitions have been detected in both 2Pi1/2 and 2Pi3/2 spin components but no fine structure transitions between the spin components were observed. Proton hyperfine splittings were resolved on some lines. The measurements have been analyzed, subjected to a least-squares fit using an effective Hamiltonian, and the appropriate molecular parameters determined. The weakness of the spectrum and the failure of attempts to power saturate favorable lines are both consistent with a small value for the electric dipole moment for SiH.

Electronic transition moment for the B(2)II-X(2)II system of NO

NASA Technical Reports Server (NTRS)

Luque, Jorge; Crosley, David R.

1995-01-01

The upsilon' = 0-3 and 7 vibrational levels of the NO B(2)II state have been selectively excited by laser radiation. The fluorescence spectra together with calculated Franck-Condon factors and r-centroids have been used to evaluate the electronic transition moment. The results for upsilon' = 0-3 are in very good agreement with recent chemiluminescence measurements and ab initio calculations. Furthermore, the data from upsilon' = 7 have been used to extend the empirically determined moment to limits 1.23 and 1.78 A, improving agreement with experimentally determined lifetimes.

Reduced-Amide Inhibitor of Pin1 Binds in a Conformation Resembling a Twisted-Amide Transition State†

PubMed Central

Xu, Guoyan G.; Zhang, Yan; Mercedes-Camacho, Ana Y.; Etzkorn, Felicia A.

2011-01-01

The mechanism of the cell cycle regulatory peptidyl prolyl isomerase (PPIase), Pin1, was investigated using reduced-amide inhibitors designed to mimic the twisted-amide transition state. Inhibitors, R–pSer–Ψ[CH2N]–Pro–2-(indol-3-yl)-ethylamine, 1 (R = fluorenylmethoxycarbonyl, Fmoc), and 2 (R = Ac), of Pin1 were synthesized and bioassayed. Inhibitor 1 had an IC50 value of 6.3 μM, which is 4.5-fold better inhibition for Pin1 than our comparable ground state analogue, a cis-amide alkene isostere containing inhibitor. The change of Fmoc to Ac in 2 improved aqueous solubility for structural determination, and resulted in an IC50 value of 12 μM. The X-ray structure of the complex of 2 bound to Pin1 was determined to 1.76 Å resolution. The structure revealed that the reduced amide adopted a conformation similar to the proposed twisted-amide transition state of Pin1, with a trans-pyrrolidine conformation of the prolyl ring. A similar conformation of substrate would be destabilized relative to the planar amide conformation. Three additional reduced amides, with Thr replacing Ser, and l- or d-pipecolate (Pip) replacing Pro, were slightly weaker inhibitors of Pin1. PMID:21980916

Fluctuations When Driving Between Nonequilibrium Steady States

NASA Astrophysics Data System (ADS)

Riechers, Paul M.; Crutchfield, James P.

2017-08-01

Maintained by environmental fluxes, biological systems are thermodynamic processes that operate far from equilibrium without detailed-balanced dynamics. Yet, they often exhibit well defined nonequilibrium steady states (NESSs). More importantly, critical thermodynamic functionality arises directly from transitions among their NESSs, driven by environmental switching. Here, we identify the constraints on excess heat and dissipated work necessary to control a system that is kept far from equilibrium by background, uncontrolled "housekeeping" forces. We do this by extending the Crooks fluctuation theorem to transitions among NESSs, without invoking an unphysical dual dynamics. This and corresponding integral fluctuation theorems determine how much work must be expended when controlling systems maintained far from equilibrium. This generalizes thermodynamic feedback control theory, showing that Maxwellian Demons can leverage mesoscopic-state information to take advantage of the excess energetics in NESS transitions. We also generalize an approach recently used to determine the work dissipated when driving between functionally relevant configurations of an active energy-consuming complex system. Altogether, these results highlight universal thermodynamic laws that apply to the accessible degrees of freedom within the effective dynamic at any emergent level of hierarchical organization. By way of illustration, we analyze a voltage-gated sodium ion channel whose molecular conformational dynamics play a critical functional role in propagating action potentials in mammalian neuronal membranes.

State feedback control design for Boolean networks.

PubMed

Liu, Rongjie; Qian, Chunjiang; Liu, Shuqian; Jin, Yu-Fang

2016-08-26

Driving Boolean networks to desired states is of paramount significance toward our ultimate goal of controlling the progression of biological pathways and regulatory networks. Despite recent computational development of controllability of general complex networks and structural controllability of Boolean networks, there is still a lack of bridging the mathematical condition on controllability to real boolean operations in a network. Further, no realtime control strategy has been proposed to drive a Boolean network. In this study, we applied semi-tensor product to represent boolean functions in a network and explored controllability of a boolean network based on the transition matrix and time transition diagram. We determined the necessary and sufficient condition for a controllable Boolean network and mapped this requirement in transition matrix to real boolean functions and structure property of a network. An efficient tool is offered to assess controllability of an arbitrary Boolean network and to determine all reachable and non-reachable states. We found six simplest forms of controllable 2-node Boolean networks and explored the consistency of transition matrices while extending these six forms to controllable networks with more nodes. Importantly, we proposed the first state feedback control strategy to drive the network based on the status of all nodes in the network. Finally, we applied our reachability condition to the major switch of P53 pathway to predict the progression of the pathway and validate the prediction with published experimental results. This control strategy allowed us to apply realtime control to drive Boolean networks, which could not be achieved by the current control strategy for Boolean networks. Our results enabled a more comprehensive understanding of the evolution of Boolean networks and might be extended to output feedback control design.

Image Charge and Electric Field Effects on Hydrogen-like Impurity-bound Polaron Energies and Oscillator Strengths in a Quantum Dot

NASA Astrophysics Data System (ADS)

Vardanyan, L. A.; Vartanian, A. L.; Asatryan, A. L.; Kirakosyan, A. A.

2016-11-01

By using Landau-Pekar variational method, the ground and the first excited state energies and the transition frequencies between the ground and the first excited states of a hydrogen-like impurity-bound polaron in a spherical quantum dot (QD) have been studied by taking into account the image charge effect (ICE). We employ the dielectric continuum model to describe the phonon confinement effects. The oscillator strengths (OSs) of transitions from the 1 s-like state to excited states of 2 s, 2 p x , and 2 p z symmetries are calculated as functions of the applied electric field and strength of the confinement potential. We have shown that with and without image charge effect, the increase of the strength of the parabolic confinement potential leads to the increase of the oscillator strengths of 1 s - 2 p x and 1 s - 2 p z transitions. This indicates that the energy differences between 1 s- and 2 p x - as well as 1 s- and 2 p z -like states have a dominant role determining the oscillator strength. Although there is almost no difference in the oscillator strengths for transitions 1 s - 2 p x and 1 s -2 p z when the image charge effect is not taken into account, it becomes significant with the image charge effect.

Load compensation as a function of state during sleep onset.

PubMed

Gora, J; Kay, A; Colrain, I M; Kleiman, J; Trinder, J

1998-06-01

Ventilation decreases and airway resistance increases with the loss of electroencephalogram alpha activity at sleep onset. The aim of this study was to determine whether reflexive load compensation is lost immediately on the loss of alpha activity. Six healthy male subjects were studied under two conditions (load and control-no load), in three states (continuous alpha, continuous theta, and immediately after a transition from alpha to theta), and in two phases (early and late sleep onset). Ventilation and respiratory timing were measured. A comparison of loaded with control conditions indicated that loading had no effect on inspiratory minute ventilation during continuous alpha (differential effect of 0.00 l/min) and only a small, nonsignificant effect in theta immediately after phase 2 transitions (0.31 l/min), indicating a preservation of load compensation at these times. However, there were significant decreases in inspiratory minute ventilation on loaded trials during continuous theta in phase 2 (0.77 l/min) and phase 3 (1.15 l/min) and during theta immediately after a transition in phase 3 (0.87 l/min), indicating a lack of reflexive load compensation. The results indicate that, because reflex load compensation is state dependent, state-related changes in airway resistance contribute to state-related changes in ventilation during sleep onset. However, this effect was slightly delayed with transitions into theta early in sleep.

Identification of the protein folding transition state from molecular dynamics trajectories

NASA Astrophysics Data System (ADS)

Muff, S.; Caflisch, A.

2009-03-01

The rate of protein folding is governed by the transition state so that a detailed characterization of its structure is essential for understanding the folding process. In vitro experiments have provided a coarse-grained description of the folding transition state ensemble (TSE) of small proteins. Atomistic details could be obtained by molecular dynamics (MD) simulations but it is not straightforward to extract the TSE directly from the MD trajectories, even for small peptides. Here, the structures in the TSE are isolated by the cut-based free-energy profile (cFEP) using the network whose nodes and links are configurations sampled by MD and direct transitions among them, respectively. The cFEP is a barrier-preserving projection that does not require arbitrarily chosen progress variables. First, a simple two-dimensional free-energy surface is used to illustrate the successful determination of the TSE by the cFEP approach and to explain the difficulty in defining boundary conditions of the Markov state model for an entropically stabilized free-energy minimum. The cFEP is then used to extract the TSE of a β-sheet peptide with a complex free-energy surface containing multiple basins and an entropic region. In contrast, Markov state models with boundary conditions defined by projected variables and conventional histogram-based free-energy profiles are not able to identify the TSE of the β-sheet peptide.

Controlling protein molecular dynamics: How to accelerate folding while preserving the native state

NASA Astrophysics Data System (ADS)

Jensen, Christian H.; Nerukh, Dmitry; Glen, Robert C.

2008-12-01

The dynamics of peptides and proteins generated by classical molecular dynamics (MD) is described by using a Markov model. The model is built by clustering the trajectory into conformational states and estimating transition probabilities between the states. Assuming that it is possible to influence the dynamics of the system by varying simulation parameters, we show how to use the Markov model to determine the parameter values that preserve the folded state of the protein and at the same time, reduce the folding time in the simulation. We investigate this by applying the method to two systems. The first system is an imaginary peptide described by given transition probabilities with a total folding time of 1μs. We find that only small changes in the transition probabilities are needed to accelerate (or decelerate) the folding. This implies that folding times for slowly folding peptides and proteins calculated using MD cannot be meaningfully compared to experimental results. The second system is a four residue peptide valine-proline-alanine-leucine in water. We control the dynamics of the transitions by varying the temperature and the atom masses. The simulation results show that it is possible to find the combinations of parameter values that accelerate the dynamics and at the same time preserve the native state of the peptide. A method for accelerating larger systems without performing simulations for the whole folding process is outlined.

Transition rate diagrams - A new approach to the study of selective excitation processes: The spectrum of manganese in a Grimm-type glow discharge

NASA Astrophysics Data System (ADS)

Weiss, Zdeněk; Steers, Edward B. M.; Pickering, Juliet C.; Mushtaq, Sohail

2014-02-01

The emission spectra of manganese observed using a Grimm-type glow discharge in pure argon, argon with 0.3% v/v hydrogen and pure neon were studied in order to identify major excitation and ionization processes of manganese in the plasma. A new procedure is proposed, in which each observed emission line is associated with the corresponding transition between different states of the Mn atom or Mn ion, and, by considering all the observed transitions from and into a specific state, a measure of the total rate is determined at which this state is radiatively populated and depopulated. These resulting population/depopulation rates are then plotted as function of level energy. Such plots, called here “transition rate diagrams”, show the role of individual states in the formation of the observed spectrum and can be used to identify possible selective excitation processes. Also, cascade excitation by radiative decay of higher excited states can be conveniently evaluated in this way. A detailed description of the observed Mn I and Mn II spectra is given for Ar, Ar-H2 and Ne plasmas and relevant excitation/ionization mechanisms are discussed. Matrix effects in analysis of manganese by glow discharge spectroscopy are discussed. A list of important Mn I and Mn II lines excited in the glow discharge plasma is given.

Enhancement of Catalytic Activity of Reduced Graphene Oxide Via Transition Metal Doping Strategy

NASA Astrophysics Data System (ADS)

Lee, Hangil; Hong, Jung A.

2017-06-01

To compare the catalytic oxidation activities of reduced graphene oxide (rGO) and rGO samples doped with five different transition metals (TM-rGO), we determine their effects on the oxidation of L-cysteine (Cys) in aqueous solution by performing electrochemistry (EC) measurements and on the photocatalytic oxidation of Cys by using high-resolution photoemission spectroscopy (HRPES) under UV illumination. Our results show that Cr-, Fe-, and Co-doped rGO with 3+ charge states (stable oxide forms: Cr3+, Fe3+, and Co3+) exhibit enhanced catalytic activities that are due to the charge states of the doped metal ions as we compare them with Cr-, Fe-, and Co-doped rGO with 2+ charge states.

Nonlinear signaling on biological networks: The role of stochasticity and spectral clustering

NASA Astrophysics Data System (ADS)

Hernandez-Hernandez, Gonzalo; Myers, Jesse; Alvarez-Lacalle, Enrique; Shiferaw, Yohannes

2017-03-01

Signal transduction within biological cells is governed by networks of interacting proteins. Communication between these proteins is mediated by signaling molecules which bind to receptors and induce stochastic transitions between different conformational states. Signaling is typically a cooperative process which requires the occurrence of multiple binding events so that reaction rates have a nonlinear dependence on the amount of signaling molecule. It is this nonlinearity that endows biological signaling networks with robust switchlike properties which are critical to their biological function. In this study we investigate how the properties of these signaling systems depend on the network architecture. Our main result is that these nonlinear networks exhibit bistability where the network activity can switch between states that correspond to a low and high activity level. We show that this bistable regime emerges at a critical coupling strength that is determined by the spectral structure of the network. In particular, the set of nodes that correspond to large components of the leading eigenvector of the adjacency matrix determines the onset of bistability. Above this transition the eigenvectors of the adjacency matrix determine a hierarchy of clusters, defined by its spectral properties, which are activated sequentially with increasing network activity. We argue further that the onset of bistability occurs either continuously or discontinuously depending upon whether the leading eigenvector is localized or delocalized. Finally, we show that at low network coupling stochastic transitions to the active branch are also driven by the set of nodes that contribute more strongly to the leading eigenvector. However, at high coupling, transitions are insensitive to network structure since the network can be activated by stochastic transitions of a few nodes. Thus this work identifies important features of biological signaling networks that may underlie their biological function.

Metastability and instability of organic crystalline substances.

PubMed

Randzio, Stanislaw L; Kutner, Andrzej

2008-02-07

Discovery of an unexpected and thermodynamically paradoxical transition from a crystalline state to an amorphous dense glassy state induced in pure organic substances by a direct absorption of a quantity of heat under atmospheric pressure and its detailed analysis performed with the use of a sensitive scanning transitiometer are described. The obtained results present first experimental precise evidence for understanding the mechanism of such a structural instability of crystalline substances in the form of c-a transition. The observed c-a transition is a purely physical phenomenon, occurring between two nonequilibrium states, a metastable crystalline phase and a dense glass, occurring through a local transient phenomenon of virtual melting. The metastable state of a crystalline substance can be caused by existence of a number of crystalline imperfections created either during crystallization or by external actions. By measuring extremely sensitive energetic effects, we found the present method to be helpful for quantitative determination of the critical number of imperfections in a crystalline solid, which make it metastable and for an indication under which conditions such a metastable crystalline form becomes unstable. By performing the transitiometric analysis of c-a transitions with two polymorphs of rosiglitazone maleate, we demonstrated to what extent this analysis is important in investigation of stability of crystalline components of drugs.

Measurement of crossflow vortices, attachment-line flow, and transition using microthin hot films

NASA Technical Reports Server (NTRS)

Mangalam, S. M.; Agarwal, N. K.; Maddalon, D. V.; Saric, W. S.

1990-01-01

A flow diagnostic experiment was conducted on a 45-deg swept-wing model using surface-mounted, multielement, microthin, hot-film sensors. The cross-flow vortex spacing, the attachment-line flow characteristics, and the transition region were all determined using an advanced data acquisition and instrumentation system. In addition to the frequencies of traveling waves predicted by linear stability theory, amplified disturbances at much higher frequencies were observed. Simultaneous measurements from sensors located at a number of chord and span locations highlighted the strong three-dimensionality of the boundary-layer flow in the presence of cross-flow vortices. The state of the attachment-line boundary layer was determined using a multielement sensor wrapped around the wing leading edge. The transition region flow characteristics were also identified.

Crossflow Stability and Transition Experiments in Swept-Wing Flow

NASA Technical Reports Server (NTRS)

Dagenhart, J. Ray; Saric, William S.

1999-01-01

An experimental examination of crossflow instability and transition on a 45deg swept wing was conducted in the Arizona State University Unsteady Wind Tunnel. The stationary-vortex pattern and transition location are visualized by using both sublimating chemical and liquid-crystal coatings. Extensive hot-wire measurements were obtained at several measurement stations across a single vortex track. The mean and travelling wave disturbances were measured simultaneously. Stationary crossflow disturbance profiles were determined by subtracting either a reference or a span-averaged velocity profile from the mean velocity data. Mean, stationary crossflow, and traveling wave velocity data were presented as local boundary layer profiles and contour plots across a single stationary crossflow vortex track. Disturbance mode profiles and growth rates were determined. The experimental data are compared with predictions from linear stability theory.

Quantum mechanical design of enzyme active sites.

PubMed

Zhang, Xiyun; DeChancie, Jason; Gunaydin, Hakan; Chowdry, Arnab B; Clemente, Fernando R; Smith, Adam J T; Handel, T M; Houk, K N

2008-02-01

The design of active sites has been carried out using quantum mechanical calculations to predict the rate-determining transition state of a desired reaction in presence of the optimal arrangement of catalytic functional groups (theozyme). Eleven versatile reaction targets were chosen, including hydrolysis, dehydration, isomerization, aldol, and Diels-Alder reactions. For each of the targets, the predicted mechanism and the rate-determining transition state (TS) of the uncatalyzed reaction in water is presented. For the rate-determining TS, a catalytic site was designed using naturalistic catalytic units followed by an estimation of the rate acceleration provided by a reoptimization of the catalytic site. Finally, the geometries of the sites were compared to the X-ray structures of related natural enzymes. Recent advances in computational algorithms and power, coupled with successes in computational protein design, have provided a powerful context for undertaking such an endeavor. We propose that theozymes are excellent candidates to serve as the active site models for design processes.

Predictability of Circulation Transitions (Observed and Modeled): Non-diffusive Dynamics, Markov Chains and Error Growth.

NASA Astrophysics Data System (ADS)

Straus, D. M.

2006-12-01

The transitions between portions of the state space of the large-scale flow is studied from daily wintertime data over the Pacific North America region using the NCEP reanalysis data set (54 winters) and very large suites of hindcasts made with the COLA atmospheric GCM with observed SST (55 members for each of 18 winters). The partition of the large-scale state space is guided by cluster analysis, whose statistical significance and relationship to SST is reviewed (Straus and Molteni, 2004; Straus, Corti and Molteni, 2006). The determination of the global nature of the flow through state space is studied using Markov Chains (Crommelin, 2004). In particular the non-diffusive part of the flow is contrasted in nature (small data sample) and the AGCM (large data sample). The intrinsic error growth associated with different portions of the state space is studied through sets of identical twin AGCM simulations. The goal is to obtain realistic estimates of predictability times for large-scale transitions that should be useful in long-range forecasting.

Infrared and far-infrared laser magnetic resonance spectroscopy of the GeH radical - Determination of ground state parameters

NASA Technical Reports Server (NTRS)

Brown, J. M.; Evenson, K. M.; Sears, T. J.

1985-01-01

The GeH radical has been detected in its ground 2 Pi state in the gas phase reaction of fluorine atoms with GeH4 by laser magnetic resonance techniques. Rotational transitions within both 2 Pi 1/2 and 2 Pi 3/2 manifolds have been observed at far-infrared wavelengths and rotational transitions between the two fine structure components have been detected at infrared wavelengths (10 microns). Signals have been observed for all five naturally occurring isotopes of germanium. Nuclear hyperfine structure for H-1 and Ge-73 has also been observed. The data for the dominant isotope (/Ge-74/H) have been fitted to within experimental error by an effective Hamiltonian to give a set of molecular parameters for the X 2 Pi state which is very nearly complete. In addition, the dipole moment of GeH in its ground state has been estimated from the relative intensities of electric and magnetic dipole transitions in the 10 micron spectrum to be 1.24(+ or - 0.10) D.

High-order multipole radiation from quantum Hall states in Dirac materials

NASA Astrophysics Data System (ADS)

Gullans, Michael J.; Taylor, Jacob M.; Imamoǧlu, Ataç; Ghaemi, Pouyan; Hafezi, Mohammad

2017-06-01

We investigate the optical response of strongly disordered quantum Hall states in two-dimensional Dirac materials and find qualitatively different effects in the radiation properties of the bulk versus the edge. We show that the far-field radiation from the edge is characterized by large multipole moments (>50 ) due to the efficient transfer of angular momentum from the electrons into the scattered light. The maximum multipole transition moment is a direct measure of the coherence length of the edge states. Accessing these multipole transitions would provide new tools for optical spectroscopy and control of quantum Hall edge states. On the other hand, the far-field radiation from the bulk appears as random dipole emission with spectral properties that vary with the local disorder potential. We determine the conditions under which this bulk radiation can be used to image the disorder landscape. Such optical measurements can probe submicron-length scales over large areas and provide complementary information to scanning probe techniques. Spatially resolving this bulk radiation would serve as a novel probe of the percolation transition near half filling.

Detecting phase boundaries of quantum spin-1/2 XXZ ladder via bipartite and multipartite entanglement transitions

NASA Astrophysics Data System (ADS)

Singha Roy, Sudipto; Dhar, Himadri Shekhar; Rakshit, Debraj; Sen(De), Aditi; Sen, Ujjwal

2017-12-01

Phase transition in quantum many-body systems inevitably causes changes in certain physical properties which then serve as potential indicators of critical phenomena. Besides the traditional order parameters, characterization of quantum entanglement has proven to be a computationally efficient and successful method for detection of phase boundaries, especially in one-dimensional models. Here we determine the rich phase diagram of the ground states of a quantum spin-1/2 XXZ ladder by analyzing the variation of bipartite and multipartite entanglements. Our study characterizes the different ground state phases and notes the correspondence with known results, while highlighting the finer details that emerge from the behavior of ground state entanglement. Analysis of entanglement in the ground state provides a clearer picture of the complex ground state phase diagram of the system using only a moderate-size model.

High spin states in {sup 151,153}Pr, {sup 157}Sm, and {sup 93}Kr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, J. K.; Ramayya, A. V.; Hamilton, J. H.

2010-09-15

High spin states are observed for the first time in the neutron-rich nuclei {sup 151,153}Pr, {sup 157}Sm, and {sup 93}Kr from the spontaneous fission of {sup 252}Cf. Twenty new transitions in {sup 151}Pr, twelve in {sup 153}Pr, five in {sup 157}Sm, and four in {sup 93}Kr were identified by using x-ray(Pr/Sm)-{gamma}-{gamma} and {gamma}-{gamma}-{gamma} triple coincidences. From the measured total internal conversion coefficients {alpha}{sub T} of four low-energy transitions in {sup 151,153}Pr, we determine that two bands in each nucleus have opposite parity. The interlacing E1 transitions between the bands suggest a form of parity doubling in {sup 151,153}Pr. New bandsmore » in {sup 157}Sm and {sup 93}Kr are reported. The half-life of the 354.8 keV state in {sup 93}Kr is measured to be 10(2) ns.« less

VizieR Online Data Catalog: Extensive linelist of CH in stellar atmospheres (Masseron+, 2014)

NASA Astrophysics Data System (ADS)

Masseron, T.; Plez, B.; van Eck, S.; Colin, R.; Daoutidis, I.; Godefroid, M.; Coheur, P.-F.; Bernath, P.; Jorissen, A.; Christlieb, N.

2014-10-01

Linelist for the CH molecules is presented. This includes the A-X, B-X, and C-X electronic transitions up to the last observed vibrational levels (i.e. v>=5 for the X and A states, v>=1 for the B state, and v>=2 for the C state), with rotational levels up to the dissociation energy as listed in Table 13. Concerning the 13CH linelists, for the vibrational levels that could not be observed but that exist for 12CH ( i.e. X2\\Δv=4 and 5, A2\\Δv=4 and 5, and C2\\{Sigma}+ v=1 and 2), the Born-Oppenheimer approximation from 12CH has been used to determine the transitions. The X-X ro-vibrational transitions up to dissociation are also included for both isotopologues. The linelist is available on http://www.astro.ulb.ac.be/~spectrotools/, and will be made available through the VALD database. (1 data file).

Transit traverse in Missouri, 1900-1937. Part 7, Central Missouri, 1902-37

USGS Publications Warehouse

Staack, John George

1940-01-01

This bulletin, which for convenience is to be published in eight parts, contains the results of all transit traverse* done In Missouri through 1937 by the Geological Survey, United States Department of the Interior, including those heretofore published. (See page X.) Each of the parts deals with one of eight sections into which the State has been divided for this purpose and which have been designated northeastern, northwestern, southeastern, southwestern, central, east-central, south-central, and west-central Missouri. In each part descriptions of the points for which geodetic positions have been determined are listed according to the quadrangles in which the points occur. Results of transit traverse other than that done by the Geological Survey have not been included.Central Missouri, as the term is used in this bulletin and as the subject of part 7 of the bulletin, is that section of the State lying between latitudes 36°00' and 39°30' and between longitudes 92°00' and 93°30'.

Transit traverse in Missouri, 1900-1937. Part 8, West-central Missouri, 1906-37

USGS Publications Warehouse

Staack, John G.

1940-01-01

This bulletin, which for convenience is to be published in eight parts, contains the results of all transit traverse* done In Missouri through 1937 by the Geological Survey, United States Department of the Interior, including those heretofore published. (See page X.) Each of the parts deals with one of eight sections into which the State has been divided for this purpose and which have been designated northeastern, northwestern, southeastern, southwestern, central, east-central, south-central, and west-central Missouri. In each part descriptions of the points for which geodetic positions have been determined are listed according to the quadrangles in which the points occur. Results of transit traverse other than that done by the Geological Survey have not been included.West-central Missouri, as the term is used in this bulletin and as the subject of part 8 of the bulletin, is that section of the State lying between latitudes 38°00' and 39°30' and west of longitude 93°30'.

Transitions between states of labor-force participation among older Israelis.

PubMed

Achdut, Leah; Tur-Sinai, Aviad; Troitsky, Rita

2015-03-01

The study examines the labor-force behavior of Israelis at older ages, focusing on the determinants of the transitions between states of labor-force participation between 2005 and 2010. The study uses panel data from the first two waves of the SHARE-Israel longitudinal survey. A multinomial logit model is used to examine the impact of sociodemographic characteristics, health state, and economic resources on labor-force transitions of people aged 50-67. The results emphasize the role of age and poor health in "pushing" older people out of the labor force or "keeping" them there. Spouse's participation is found to encourage individuals to leave the labor force or to refrain from joining it. However, living with a participating spouse is negatively associated with staying out of the labor force, consistent with the dominance of the complementarity of leisure effect found in the literature. Wealth as an economic resource available to individuals for retirement is also found to encourage individuals to leave the labor force or to refrain from joining it.

Direct calculation of liquid-vapor phase equilibria from transition matrix Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Errington, Jeffrey R.

2003-06-01

An approach for directly determining the liquid-vapor phase equilibrium of a model system at any temperature along the coexistence line is described. The method relies on transition matrix Monte Carlo ideas developed by Fitzgerald, Picard, and Silver [Europhys. Lett. 46, 282 (1999)]. During a Monte Carlo simulation attempted transitions between states along the Markov chain are monitored as opposed to tracking the number of times the chain visits a given state as is done in conventional simulations. Data collection is highly efficient and very precise results are obtained. The method is implemented in both the grand canonical and isothermal-isobaric ensemble. The main result from a simulation conducted at a given temperature is a density probability distribution for a range of densities that includes both liquid and vapor states. Vapor pressures and coexisting densities are calculated in a straightforward manner from the probability distribution. The approach is demonstrated with the Lennard-Jones fluid. Coexistence properties are directly calculated at temperatures spanning from the triple point to the critical point.

Spectroscopic properties of HoAl3(BO3)4 single crystal

NASA Astrophysics Data System (ADS)

Ikonnikov, D. A.; Malakhovskii, A. V.; Sukhachev, A. L.; Temerov, V. L.; Krylov, A. S.; Bovina, A. F.; Aleksandrovsky, A. S.

2014-11-01

The Judd-Ofelt theory has been applied to analyze absorption spectra of Ho3+ ion in HoAl3(BO3)4 measured in spectral range 300-700 nm at room temperature. The Judd-Ofelt spectroscopic parameters have been determined as: Ω2 = 18.87 × 10-20 cm2, Ω4 = 17.04 × 10-20 cm2, Ω6 = 9.21 × 10-20 cm2. These parameters have been used to calculate radiative lifetimes and branching ratios of the luminescence manifolds. Three luminescent bands were found in the spectral range 450-700 nm ascribed to transitions from the 5F5, (5F4, 5S2) and 3K8 states to the ground state 5I8. Experimental intensities of these luminescence transitions were compared with those calculated by using Judd-Ofelt theory and the system of kinetic equations for populations of starting luminescing states. Probabilities of radiativeless transitions were evaluated from this comparison.

Vibrational spectroscopic study on polymorphism of erucic acid and palmitoleic acid: γ1→α1 and γ→α reversible solid state phase transitions

NASA Astrophysics Data System (ADS)

Kaneko, Fumitoshi; Yamazaki, Kazuhiro; Kobayashi, Masamichi; Sato, Kiyotaka; Suzuki, Masao

1994-08-01

The infrared and Raman spectra of four polymorphic phases (α, α1, γ and γ1) of erucic acid ( cis-13-docosenoic acid) and those of two polymorphic phases (α and γ) of palmitoleic acid ( cis-9-hexadecenoic acid) were investigated. The γ and γ1 phases of erucic acid were analyzed on the basis of crystal structures determined by us. There were large spectral differences between γ and γ1 phases, which could be ascribed to the differences in the conformation of cis-olefin groups and the subcell structure. Two types of reversible solid state phase transitions (γ→α and γ1→α1 transitions) were followed by the infrared and Raman spectra. It was concluded that the mechanism of the γ→α phase transition of erucic and palmitoleic acids is essentially the same as that of oleic acid previously reported by us [ J. Phys. Chem.90, 6371 (1986)], i.e. this phase transition is of order-disorder type accompanied by a conformational disordering at the methyl-terminal chain. Spectral changes on the γ1→α1 transition suggested that a similar structural change took place during this transition but there were large structural differences between α and α1.

Markov Transition Model to Dementia with Death as a Competing Event.

PubMed

Wei, Shaoceng; Xu, Liou; Kryscio, Richard J

2014-12-01

This study evaluates the effect of death as a competing event to the development of dementia in a longitudinal study of the cognitive status of elderly subjects. A multi-state Markov model with three transient states: intact cognition, mild cognitive impairment (M.C.I.) and global impairment (G.I.) and one absorbing state: dementia is used to model the cognitive panel data; transitions among states depend on four covariates age, education, prior state (intact cognition, or M.C.I., or G.I.) and the presence/absence of an apolipoprotein E-4 allele (APOE4). A Weibull model and a Cox proportional hazards (Cox PH) model are used to fit the survival from death based on age at entry and the APOE4 status. A shared random effect correlates this survival time with the transition model. Simulation studies determine the sensitivity of the maximum likelihood estimates to the violations of the Weibull and Cox PH model assumptions. Results are illustrated with an application to the Nun Study, a longitudinal cohort of 672 participants 75+ years of age at baseline and followed longitudinally with up to ten cognitive assessments per nun.

Markov Transition Model to Dementia with Death as a Competing Event

PubMed Central

Wei, Shaoceng; Xu, Liou; Kryscio, Richard J.

2014-01-01

This study evaluates the effect of death as a competing event to the development of dementia in a longitudinal study of the cognitive status of elderly subjects. A multi-state Markov model with three transient states: intact cognition, mild cognitive impairment (M.C.I.) and global impairment (G.I.) and one absorbing state: dementia is used to model the cognitive panel data; transitions among states depend on four covariates age, education, prior state (intact cognition, or M.C.I., or G.I.) and the presence/absence of an apolipoprotein E-4 allele (APOE4). A Weibull model and a Cox proportional hazards (Cox PH) model are used to fit the survival from death based on age at entry and the APOE4 status. A shared random effect correlates this survival time with the transition model. Simulation studies determine the sensitivity of the maximum likelihood estimates to the violations of the Weibull and Cox PH model assumptions. Results are illustrated with an application to the Nun Study, a longitudinal cohort of 672 participants 75+ years of age at baseline and followed longitudinally with up to ten cognitive assessments per nun. PMID:25110380

Numerical study of the effects of surface topography and chemistry on the wetting transition using the string method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yanan, E-mail: ynzhang@suda.edu.cn; Ren, Weiqing, E-mail: matrw@nus.edu.sg; Institute of High Performance Computing, Singapore 138632

2014-12-28

Droplets on a solid surface patterned with microstructures can exhibit the composite Cassie-Baxter (CB) state or the wetted Wenzel state. The stability of the CB state is determined by the energy barrier separating it from the wetted state. In this work, we study the CB to Wenzel transition using the string method [E et al., J. Chem. Phys. 126, 164103 (2007); W. Ren and E. Vanden-Eijnden, J. Chem. Phys. 138, 134105 (2013)]. We compute the transition states and energy barriers for a three-dimensional droplet on patterned surfaces. The liquid-vapor coexistence is modeled using the mean field theory. Numerical results aremore » obtained for surfaces patterned with straight pillars and nails, respectively. It is found that on both type of surfaces, wetting occurs via infiltration of the liquid in a single groove. The reentrant geometry of nails creates large energy barrier for the wetting of the solid surface compared to straight pillars. We also study the effect of surface chemistry, pillar height, and inter-pillar spacing on the energy barrier and compare it with nails.« less

Ground-state and pairing-vibrational bands with equal quadrupole collectivity in 124Xe

NASA Astrophysics Data System (ADS)

Radich, A. J.; Garrett, P. E.; Allmond, J. M.; Andreoiu, C.; Ball, G. C.; Bianco, L.; Bildstein, V.; Chagnon-Lessard, S.; Cross, D. S.; Demand, G. A.; Diaz Varela, A.; Dunlop, R.; Finlay, P.; Garnsworthy, A. B.; Hackman, G.; Hadinia, B.; Jigmeddorj, B.; Laffoley, A. T.; Leach, K. G.; Michetti-Wilson, J.; Orce, J. N.; Rajabali, M. M.; Rand, E. T.; Starosta, K.; Sumithrarachchi, C. S.; Svensson, C. E.; Triambak, S.; Wang, Z. M.; Wood, J. L.; Wong, J.; Williams, S. J.; Yates, S. W.

2015-04-01

The nuclear structure of 124Xe has been investigated via measurements of the β+/EC decay of 124Cs with the 8 π γ -ray spectrometer at the TRIUMF-ISAC facility. The data collected have enabled branching ratio measurements of weak, low-energy transitions from highly excited states, and the 2+→0+ in-band transitions have been observed. Combining these results with those from a previous Coulomb excitation study, B (E 2 ;23+→02+) =78 (13 ) W.u. and B (E 2 ;24+→03+) =53 (12 ) W.u. were determined. The 03+ state, in particular, is interpreted as the main fragment of the proton-pairing vibrational band identified in a previous 122Te (3He,n )124Xe measurement, and has quadrupole collectivity equal to, within uncertainty, that of the ground-state band.

Reliability assessment of fiber optic communication lines depending on external factors and diagnostic errors

NASA Astrophysics Data System (ADS)

Bogachkov, I. V.; Lutchenko, S. S.

2018-05-01

The article deals with the method for the assessment of the fiber optic communication lines (FOCL) reliability taking into account the effect of the optical fiber tension, the temperature influence and the built-in diagnostic equipment errors of the first kind. The reliability is assessed in terms of the availability factor using the theory of Markov chains and probabilistic mathematical modeling. To obtain a mathematical model, the following steps are performed: the FOCL state is defined and validated; the state graph and system transitions are described; the system transition of states that occur at a certain point is specified; the real and the observed time of system presence in the considered states are identified. According to the permissible value of the availability factor, it is possible to determine the limiting frequency of FOCL maintenance.

0 - π Quantum transition in a carbon nanotube Josephson junction: Universal phase dependence and orbital degeneracy

NASA Astrophysics Data System (ADS)

Delagrange, R.; Weil, R.; Kasumov, A.; Ferrier, M.; Bouchiat, H.; Deblock, R.

2018-05-01

In a quantum dot hybrid superconducting junction, the behavior of the supercurrent is dominated by Coulomb blockade physics, which determines the magnetic state of the dot. In particular, in a single level quantum dot singly occupied, the sign of the supercurrent can be reversed, giving rise to a π-junction. This 0 - π transition, corresponding to a singlet-doublet transition, is then driven by the gate voltage or by the superconducting phase in the case of strong competition between the superconducting proximity effect and Kondo correlations. In a two-level quantum dot, such as a clean carbon nanotube, 0- π transitions exist as well but, because more cotunneling processes are allowed, are not necessarily associated to a magnetic state transition of the dot. In this proceeding, after a review of 0- π transitions in Josephson junctions, we present measurements of current-phase relation in a clean carbon nanotube quantum dot, in the single and two-level regimes. In the single level regime, close to orbital degeneracy and in a regime of strong competition between local electronic correlations and superconducting proximity effect, we find that the phase diagram of the phase-dependent transition is a universal characteristic of a discontinuous level-crossing quantum transition at zero temperature. In the case where the two levels are involved, the nanotube Josephson current exhibits a continuous 0 - π transition, independent of the superconducting phase, revealing a different physical mechanism of the transition.

Magnetic Phase Transitions in NdCoAsO

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGuire, Michael A; Gout, Delphine J; Garlea, Vasile O

2010-01-01

NdCoAsO undergoes three magnetic phase transitions below room temperature. Here we report the results of our experimental investigation of this compound, including determination of the crystal and magnetic structures using powder neutron diffraction, as well as measurements of electrical resistivity, thermal conductivity, Seebeck coefficient, magnetization, and heat capacity. These results show that upon cooling a ferromagnetic state emerges near 69 K with a small saturation moment of -0.2{micro}{sub B}, likely on Co atoms. At 14 K the material enters an antiferromagnetic state with propagation vector (0 0 1/2) and small ordered moments (-0.4{micro}{sub B}) on Co and Nd. Near 3.5more » K a third transition is observed, and corresponds to the antiferromagnetic ordering of larger moments on Nd, with the same propagation vector. The ordered moment on Nd reaches 1.39(5){micro}{sub B} at 300 mK. Anomalies in the magnetization, electrical resistivity, and heat capacity are observed at all three magnetic phase transitions.« less

Entanglement scaling at first order quantum phase transitions

NASA Astrophysics Data System (ADS)

Yuste, A.; Cartwright, C.; De Chiara, G.; Sanpera, A.

2018-04-01

First order quantum phase transitions (1QPTs) are signalled, in the thermodynamic limit, by discontinuous changes in the ground state properties. These discontinuities affect expectation values of observables, including spatial correlations. When a 1QPT is crossed in the vicinity of a second order one, due to the correlation length divergence of the latter, the corresponding ground state is modified and it becomes increasingly difficult to determine the order of the transition when the size of the system is finite. Here we show that, in such situations, it is possible to apply finite size scaling (FSS) to entanglement measures, as it has recently been done for the order parameters and the energy gap, in order to recover the correct thermodynamic limit (Campostrini et al 2014 Phys. Rev. Lett. 113 070402). Such a FSS can unambiguously discriminate between first and second order phase transitions in the vicinity of multicritical points even when the singularities displayed by entanglement measures lead to controversial results.

High-spin level structure and Ground-state phase transition in the odd-mass 103-109Rh isotopes in the framework of exactly solvable sdg interacting boson-fermion model

NASA Astrophysics Data System (ADS)

Ghapanvari, M.; Ghorashi, A. H.; Ranjbar, Z.; Jafarizadeh, M. A.

2018-03-01

In this article, the negative-parity states in the odd-mass 103 - 109Rh isotopes in terms of the sd and sdg interacting-boson fermion models were studied. The transitional interacting boson-fermion model Hamiltonians in sd and sdg-IBFM versions based on affine SU (1 , 1) Lie Algebra were employed to describe the evolution from the spherical to deformed gamma unstable shapes along with the chain of Rh isotopes. In this method, sdg-IBFM Hamiltonian, which is a three level pairing Hamiltonian was determined easily via the exactly solvable method. Some observables of the shape phase transitions such as energy levels, the two neutron separation energies, signature splitting of the γ-vibrational band, the α-decay and double β--decay energies were calculated and examined for these isotopes. The present calculation correctly reproduces the spherical to gamma-soft phase transition in the Rh isotopes. Some comparisons were made with sd-IBFM.

Analysis of the behavior of a wiper blade around the reversal in consideration of dynamic and static friction

NASA Astrophysics Data System (ADS)

Unno, M.; Shibata, A.; Yabuno, H.; Yanagisawa, D.; Nakano, T.

2017-04-01

Reducing noise generated by automobile windshield wipers during reversals is a desirable feature. For this purpose, details of the behavior of the wiper blade need to be ascertained. In this study, we present theoretical and experimental clarification of this behavior during reversals. Using simulation algorithms to consider exactly the effects of dynamic and static friction, we determined theoretical predictions for the vibrational response caused by friction and the response frequency and compared these results with experimental ones obtained from a mock-up incorporating an actual wiper blade. We introduce an analytical link model with two degrees of freedom and consider two types of states at the blade tip. In the stick and the slip states, static friction and dynamic friction, respectively, act on the blade tip. In the theoretical approach, the static friction is expressed by a set-valued function. The transition between the two states is repeated and an evaluation of an exact transition time leads to an accurate prediction of the behavior of the wiper system. In the analysis, the slack variable method is used to find the exact transition time. Assuming low blade speeds during reversal, a parameter study indicates that the blade tip transitions between slip and stick states and the frequency of the vibration caused by this transitions is close to the natural frequency of the neck of the wiper blade. The theoretical predictions are in good agreement with experimental observations.

Contactless electroreflectance study of strained Zn0.79Cd0.21Se/ZnSe double quantum wells

NASA Astrophysics Data System (ADS)

Tu, R. C.; Su, Y. K.; Lin, D. Y.; Li, C. F.; Huang, Y. S.; Lan, W. H.; Tu, S. L.; Chang, S. J.; Chou, S. C.; Chou, W. C.

1998-01-01

We have studied various excitonic transitions of strained Zn0.79Cd0.21Se/ZnSe double quantum wells, grown by molecular beam epitaxy on (100) GaAs substrates, using contactless electroreflectance (CER) at 15 and 300 K. A number of intersub-band transitions in the CER spectra from the sample have been observed. An analysis of the CER spectra has led to the identification of various excitonic transitions, mnH(L), between the mth conduction band state and the nth heavy (light)-hole band state. The conduction-band offset Qc is used as an adjustable parameter to study the band offset in the strained Zn0.79Cd0.21Se/ZnSe system. The value of Qc is determined to be 0.67±0.03.

Dehydration of detomidine hydrochloride monohydrate.

PubMed

Veldre, K; Actiņš, A; Jaunbergs, J

2011-10-09

The thermodynamic stability of detomidine hydrochloride monohydrate has been evaluated on the basis of phase transition kinetics in solid state. A method free of empirical models was used for the treatment of kinetic data, and compared to several known solid state kinetic data processing methods. Phase transitions were monitored by powder X-ray diffraction (PXRD) and thermal analysis. Full PXRD profiles were used for determining the phase content instead of single reflex intensity measurements, in order to minimize the influence of particle texture. We compared the applicability of isothermal and nonisothermal methods to our investigation of detomidine hydrochlorine monohydrate dehydration. Copyright © 2011 Elsevier B.V. All rights reserved.

A United States regulator's perspective on the ongoing chlorofluorocarbon transition.

PubMed

Meyer, R J

1999-12-01

The Food and Drug Administration (FDA) put in place a general ban on the use of chlorofluorocarbons for the products it regulates (medical devices, drugs, and foods) in 1978, exempting those products where chlorofluorocarbon use was determined to be essential for the public health. In the intervening years, as the international commitment to a full transition away from all chlorofluorocarbon use took shape under the Montreal Protocol, the FDA has worked with industry to facilitate the development and testing of alternative technologies and products for inhalation drug products. As these alternative products begin to move from testing through the approval process and into marketing, the FDA is working collaboratively with the Environmental Protection Agency, other governmental agencies, and nongovernmental stakeholders to develop a transition policy for the United States. The transition policy for metered dose inhalers must be one that achieves the dual aims of first protecting the patients who rely on these vital medical products, while also achieving the public health need of protecting the ozone layer. As a part of developing such a transition strategy, the FDA published an advance notice of proposed rulemaking (ANPRM) in March 1997. The ANPRM proposed mechanisms by which the FDA could determine when chlorofluorocarbon use in a drug product could no longer be considered essential. The ANPRM resulted in a large amount of valuable public debate and input. The FDA is now working to incorporate the knowledge gained from these public comments as it continues the rule-making process.

Hawaii State Plan for Occupational Safety and Health. Final rule.

PubMed

2012-09-21

This document announces the Occupational Safety and Health Administration's (OSHA) decision to modify the Hawaii State Plan's ``final approval'' determination under Section 18(e) of the Occupational Safety and Health Act (the Act) and to transition to ``initial approval'' status. OSHA is reinstating concurrent federal enforcement authority over occupational safety and health issues in the private sector, which have been solely covered by the Hawaii State Plan since 1984.

Morphological transitions of brain sphingomyelin are determined by the hydration protocol: ripples re-arrange in plane, and sponge-like networks disintegrate into small vesicles.

PubMed

Meyer, H W; Bunjes, H; Ulrich, A S

1999-06-01

The phase transition of hydrated brain sphingomyelin occurs at around 35 degrees C, which is close to the physiological temperature. Freeze-fracture electron microscopy is used to characterize different gel state morphologies in terms of solid-ordered and liquid-ordered phase states, according to the occurrence of ripples and other higher-dimensional bilayer deformations. Evidently, the natural mixed-chain sphingomyelin does not assume the flat L beta, phase but instead the rippled P beta, phase, with symmetric and asymmetric ripples as well as macroripples and an egg-carton pattern, depending on the incubation conditions. An unexpected difference was observed between samples that are hydrated above and below the phase transition temperature. When the lipid is hydrated at low temperature, a sponge-like network of bilayers is formed in the gel state, next to some normal lamellae. The network loses its ripples during cold-incubation, which indicates the formation of a liquid-ordered (lo) gel phase. Ripples re-appear upon warming and the sponge-like network disintegrates spontaneously and irreversibly into small vesicles above the phase transition.

Ising tricriticality in the extended Hubbard model with bond dimerization

NASA Astrophysics Data System (ADS)

Fehske, Holger; Ejima, Satoshi; Lange, Florian; Essler, Fabian H. L.

We explore the quantum phase transition between Peierls and charge-density-wave insulating states in the one-dimensional, half-filled, extended Hubbard model with explicit bond dimerization. We show that the critical line of the continuous Ising transition terminates at a tricritical point, belonging to the universality class of the tricritical Ising model with central charge c=7/10. Above this point, the quantum phase transition becomes first order. Employing a numerical matrix-product-state based (infinite) density-matrix renormalization group method we determine the ground-state phase diagram, the spin and two-particle charge excitations gaps, and the entanglement properties of the model with high precision. Performing a bosonization analysis we can derive a field description of the transition region in terms of a triple sine-Gordon model. This allows us to derive field theory predictions for the power-law (exponential) decay of the density-density (spin-spin) and bond-order-wave correlation functions, which are found to be in excellent agreement with our numerical results. This work was supported by Deutsche Forschungsgemeinschaft (Germany), SFB 652, project B5, and by the EPSRC under Grant No. EP/N01930X/1 (FHLE).

Reducing sojourn points from recurrence plots to improve transition detection: Application to fetal heart rate transitions.

PubMed

Zaylaa, Amira; Charara, Jamal; Girault, Jean-Marc

2015-08-01

The analysis of biomedical signals demonstrating complexity through recurrence plots is challenging. Quantification of recurrences is often biased by sojourn points that hide dynamic transitions. To overcome this problem, time series have previously been embedded at high dimensions. However, no one has quantified the elimination of sojourn points and rate of detection, nor the enhancement of transition detection has been investigated. This paper reports our on-going efforts to improve the detection of dynamic transitions from logistic maps and fetal hearts by reducing sojourn points. Three signal-based recurrence plots were developed, i.e. embedded with specific settings, derivative-based and m-time pattern. Determinism, cross-determinism and percentage of reduced sojourn points were computed to detect transitions. For logistic maps, an increase of 50% and 34.3% in sensitivity of detection over alternatives was achieved by m-time pattern and embedded recurrence plots with specific settings, respectively, and with a 100% specificity. For fetal heart rates, embedded recurrence plots with specific settings provided the best performance, followed by derivative-based recurrence plot, then unembedded recurrence plot using the determinism parameter. The relative errors between healthy and distressed fetuses were 153%, 95% and 91%. More than 50% of sojourn points were eliminated, allowing better detection of heart transitions triggered by gaseous exchange factors. This could be significant in improving the diagnosis of fetal state. Copyright © 2014 Elsevier Ltd. All rights reserved.

Urea-temperature phase diagrams capture the thermodynamics of denatured state expansion that accompany protein unfolding

PubMed Central

Tischer, Alexander; Auton, Matthew

2013-01-01

We have analyzed the thermodynamic properties of the von Willebrand factor (VWF) A3 domain using urea-induced unfolding at variable temperature and thermal unfolding at variable urea concentrations to generate a phase diagram that quantitatively describes the equilibrium between native and denatured states. From this analysis, we were able to determine consistent thermodynamic parameters with various spectroscopic and calorimetric methods that define the urea–temperature parameter plane from cold denaturation to heat denaturation. Urea and thermal denaturation are experimentally reversible and independent of the thermal scan rate indicating that all transitions are at equilibrium and the van't Hoff and calorimetric enthalpies obtained from analysis of individual thermal transitions are equivalent demonstrating two-state character. Global analysis of the urea–temperature phase diagram results in a significantly higher enthalpy of unfolding than obtained from analysis of individual thermal transitions and significant cross correlations describing the urea dependence of and that define a complex temperature dependence of the m-value. Circular dichroism (CD) spectroscopy illustrates a large increase in secondary structure content of the urea-denatured state as temperature increases and a loss of secondary structure in the thermally denatured state upon addition of urea. These structural changes in the denatured ensemble make up ∼40% of the total ellipticity change indicating a highly compact thermally denatured state. The difference between the thermodynamic parameters obtained from phase diagram analysis and those obtained from analysis of individual thermal transitions illustrates that phase diagrams capture both contributions to unfolding and denatured state expansion and by comparison are able to decipher these contributions. PMID:23813497

Maximally reliable Markov chains under energy constraints.

PubMed

Escola, Sean; Eisele, Michael; Miller, Kenneth; Paninski, Liam

2009-07-01

Signal-to-noise ratios in physical systems can be significantly degraded if the outputs of the systems are highly variable. Biological processes for which highly stereotyped signal generations are necessary features appear to have reduced their signal variabilities by employing multiple processing steps. To better understand why this multistep cascade structure might be desirable, we prove that the reliability of a signal generated by a multistate system with no memory (i.e., a Markov chain) is maximal if and only if the system topology is such that the process steps irreversibly through each state, with transition rates chosen such that an equal fraction of the total signal is generated in each state. Furthermore, our result indicates that by increasing the number of states, it is possible to arbitrarily increase the reliability of the system. In a physical system, however, an energy cost is associated with maintaining irreversible transitions, and this cost increases with the number of such transitions (i.e., the number of states). Thus, an infinite-length chain, which would be perfectly reliable, is infeasible. To model the effects of energy demands on the maximally reliable solution, we numerically optimize the topology under two distinct energy functions that penalize either irreversible transitions or incommunicability between states, respectively. In both cases, the solutions are essentially irreversible linear chains, but with upper bounds on the number of states set by the amount of available energy. We therefore conclude that a physical system for which signal reliability is important should employ a linear architecture, with the number of states (and thus the reliability) determined by the intrinsic energy constraints of the system.

Nuclear Structure of 124Xe Studied with β+/EC-Decay

NASA Astrophysics Data System (ADS)

Radich, A. J.; Garrett, P. E.; Allmond, J. M.; Andreoiu, C.; Ball, G. C.; Bianco, L.; Bildstein, V.; Chagnon-Lessard, S.; Cross, D. S.; Diaz Varela, A.; Dunlop, R.; Finlay, P.; Garnsworthy, A. B.; Hackman, G.; Hadinia, B.; Jigmeddorj, B.; Laffoley, A. T.; Leach, K. G.; Michetti-Wilson, J.; Orce, J. N.; Rajabali, M. M.; Rand, E.; Starosta, K.; Sumithrarachchi, C. S.; Svensson, C. E.; Triambak, S.; Wang, Z. M.; Wood, J. L.; Wong, J.; Williams, S. J.; Yates, S. W.

The nuclear structure of 124Xe was investigated using γ-ray spectroscopy following the β+/EC-decay of 124Cs. A very high-statistics data set was collected and γγ coincidence data was analyzed, greatly adding to the 124Xe level scheme. A new decay branch from the high-spin isomer of 124Cs was observed as well as weak E2 transitions into excited 0+ states in 124Xe. B(E2) transition strengths of such low-spin transitions are very important in determining collective properties, which are currently poorly characterized in the region of neutron-deficient xenon isotopes.

Pressure-Induced Structural Transition and Enhancement of Energy Gap of CuAlO2

NASA Astrophysics Data System (ADS)

Nakanishi, Akitaka

2011-02-01

By using first-principles calculations, we studied the stable crystal structures and energy gaps of CuAlO2 under high pressure. Our simulation shows that CuAlO2 transforms from a delafossite structure to a leaning delafossite structure. The critical pressure of the transition was determined to be 60 GPa. The energy gap of CuAlO2 increases through the structural transition due to the enhanced covalency of Cu 3d and O 2p states. We found that a chalcopyrite structure does not appear as a stable structure under high pressure.

Correlations for Boundary-Layer Transition on Mars Science Laboratory Entry Vehicle Due to Heat-Shield Cavities

NASA Technical Reports Server (NTRS)

Hollis, Brian R.; Liechty, Derek S.

2008-01-01

The influence of cavities (for attachment bolts) on the heat-shield of the proposed Mars Science Laboratory entry vehicle has been investigated experimentally and computationally in order to develop a criterion for assessing whether the boundary layer becomes turbulent downstream of the cavity. Wind tunnel tests were conducted on the 70-deg sphere-cone vehicle geometry with various cavity sizes and locations in order to assess their influence on convective heating and boundary layer transition. Heat-transfer coefficients and boundary-layer states (laminar, transitional, or turbulent) were determined using global phosphor thermography.

Hybrid microwave/conventionally heated calorimeter

NASA Astrophysics Data System (ADS)

Binner, Jon G. P.; Price, Duncan M.; Reading, Mike; Vaidhyanathan, Bala

2005-06-01

The design and construction of a calorimeter in which the specimen may be heated by microwave radiation and/or hot air is described. The apparatus was used to examine the effect of microwave radiation on the melting of benzil (89°C) and the solid-state phase transition of silver iodide (147°C). Reproducibility of transition temperature determinations were within ±1°C. No changes were observed for benzil but silver iodide exhibited an apparent reduction in transition temperature to around 120°C in the presence of microwaves, which increased with the level of microwave irradiation.

Determination of anisotropic dipole moments in self-assembled quantum dots using Rabi oscillations

NASA Astrophysics Data System (ADS)

Muller, Andreas; Wang, Qu-Quan; Bianucci, Pablo; Xue, Qi-Kun; Shih, Chih-Kang

2004-03-01

By investigating the polarization-dependent Rabi oscillations using photoluminescence spectroscopy, we determined the respective transition dipole moments of the two excited excitonic states |Ex> and |Ey> of a single self-assembled quantum dot that are nondegenerate due to shape anisotropy. We find that the ratio of the two dipole moments is close to the physical elongation ratio of the quantum dot. We also measured the ground state radiative lifetimes of several quantum dots. The dipole moments calculated from the latter are in reasonable agreement with the dipole moments determined from the periodicity of the Rabi oscillations.

Applying threshold concepts to conservation management of dryland ecosystems: Case studies on the Colorado Plateau

USGS Publications Warehouse

Bowker, Matthew A.; Miller, Mark E.; Garman, Steven L.; Belote, Travis; Guntenspergen, Glenn R.

2014-01-01

Ecosystems may occupy functionally distinct alternative states, some of which are more or less desirable from a management standpoint. Transitions from state to state are usually associated with a particular trigger or sequence of triggers, such as the addition or subtraction of a disturbance. Transitions are often not linear, rather it is common to see an abrupt transition come about even though the trigger increases only incrementally; these are examples of threshold behaviors. An ideal monitoring program, such as the National Park Service’s Inventory and Monitoring Program, would quantify triggers, and be able to inform managers when measurements of a trigger are approaching a threshold so that management action can avoid an unwanted state transition. Unfortunately, both triggers and the threshold points at which state transitions occur are generally only partially known. Using case studies, we advance a general procedure to help identify triggers and estimate where threshold dynamics may occur. Our procedure is as follows: (1) Operationally define the ecosystem type being considered; we suggest that the ecological site concept of the Natural Resource Conservation Service is a useful system, (2) Using all available a priori knowledge to develop a state-and-transition model (STM), which defines possible ecosystem states, plausible transitions among them and likely triggers, (3) Validate the STM by verifying the existence of its states to the greatest degree possible, (4) Use the STM model to identify transitions and triggers likely to be detectable by a monitoring program, and estimate to the greatest degree possible the value of a measurable indicator of a trigger at the point that a state transition is imminent (tipping point), and values that may indicate when management intervention should be considered (assessment points). We illustrate two different methods for attaining these goals using a data-rich case study in Canyonlands National Park, and a data-poor case study in Wupatki National Monument. In the data-rich case, STMs are validated and revised, and tipping and assessment points are estimated using statistical analysis of data. In the data-poor case, we develop an iterative expert opinion survey approach to validate the degree of confidence in an STM, revise the model, identify lack of confidence in specific model components, and create reasonable first approximations of tipping and assessment points, which can later be refined when more data are available. Our goal should be to develop the best set of models possible given the level of information available to support decisions, which is often not much. The approach presented here offers a flexible means of achieving this goal, and determining specific research areas in need of study.

Catalytic transitions in the human MDR1 P-glycoprotein drug binding sites.

PubMed

Wise, John G

2012-06-26

Multidrug resistance proteins that belong to the ATP-binding cassette family like the human P-glycoprotein (ABCB1 or Pgp) are responsible for many failed cancer and antiviral chemotherapies because these membrane transporters remove the chemotherapeutics from the targeted cells. Understanding the details of the catalytic mechanism of Pgp is therefore critical to the development of inhibitors that might overcome these resistances. In this work, targeted molecular dynamics techniques were used to elucidate catalytically relevant structures of Pgp. Crystal structures of homologues in four different conformations were used as intermediate targets in the dynamics simulations. Transitions from conformations that were wide open to the cytoplasm to transition state conformations that were wide open to the extracellular space were studied. Twenty-six nonredundant transitional protein structures were identified from these targeted molecular dynamics simulations using evolutionary structure analyses. Coupled movement of nucleotide binding domains (NBDs) and transmembrane domains (TMDs) that form the drug binding cavities were observed. Pronounced twisting of the NBDs as they approached each other as well as the quantification of a dramatic opening of the TMDs to the extracellular space as the ATP hydrolysis transition state was reached were observed. Docking interactions of 21 known transport ligands or inhibitors were analyzed with each of the 26 transitional structures. Many of the docking results obtained here were validated by previously published biochemical determinations. As the ATP hydrolysis transition state was approached, drug docking in the extracellular half of the transmembrane domains seemed to be destabilized as transport ligand exit gates opened to the extracellular space.

Gas phase chemistry in gallium nitride CVD: Theoretical determination of the Arrhenius parameters for the first Ga-C bond homolysis of trimethylgallium.

PubMed

Schmid, Rochus; Basting, Daniel

2005-03-24

Experimental evidence suggests that the energy of activation for the first homolytic Ga-C bond fission of GaMe3 of Ea = 249 kJ/mol, measured by Jacko and Price in a hot-wall tube reactor, is affected by surface catalytic effects. In this contribution, the rate constant for this crucial step in the gas-phase pyrolysis of GaMe3 has been calculated by variational transition state theory. By a basis set extrapolation on the MP2/cc-pVXZ level and a correlation correction from CCSD(T)/cc-pVDZ level, a theoretical "best estimate" for the bond energy of Delta H(289K) = 327.2 kJ/mol was derived. For the VTST calculation on the B3LYP/cc-pVDZ level, the energies were corrected to reproduce this bond energy. Partition functions of the transitional modes were approximated by a hindered rotor approximation to be valid along the whole reaction coordinate defined by the Ga-C bond length. On the basis of the canonical transition state theory, reaction rates were determined using the maxima of the free energy Delta G++. An Arrhenius-type rate law was fitted to these rate constants, yielding an apparent energy of activation of Ea = 316.7 kJ/mol. The preexponential factor A = 3.13 x 10(16) 1/s is an order of magnitude larger than the experimental results because of a larger release of entropy at the transition state as compared to that of the unknown surface catalyzed mechanism.

Catastrophic shifts in vegetation-soil systems may unfold rapidly or slowly independent of the rate of change in the system driver

NASA Astrophysics Data System (ADS)

Karssenberg, Derek; Bierkens, Marc

2014-05-01

Complex systems may switch between contrasting stable states under gradual change of a driver. Such critical transitions often result in considerable long-term damage because strong hysteresis impedes reversion, and the transition becomes catastrophic. Critical transitions largely reduce our capability of forecasting future system states because it is hard to predict the timing of their occurrence [2]. Moreover, for many systems it is unknown how rapidly the critical transition unfolds when the tipping point has been reached. The rate of change during collapse, however, is important information because it determines the time available to take action to reverse a shift [1]. In this study we explore the rate of change during the degradation of a vegetation-soil system on a hillslope from a state with considerable vegetation cover and large soil depths, to a state with sparse vegetation and a bare rock or negligible soil depths. Using a distributed, stochastic model coupling hydrology, vegetation, weathering and water erosion, we derive two differential equations describing the vegetation and the soil system, and their interaction. Two stable states - vegetated and bare - are identified by means of analytical investigation, and it is shown that the change between these two states is a critical transition as indicated by hysteresis. Surprisingly, when the tipping point is reached under a very slow increase of grazing pressure, the transition between the vegetated and the bare state can either unfold rapidly, over a few years, or gradually, occurring over decennia up to millennia. These differences in the rate of change during the transient state are explained by differences in bedrock weathering rates. This finding emphasizes the considerable uncertainty associated with forecasting catastrophic shifts in ecosystems, which is due to both difficulties in forecasting the timing of the tipping point and the rate of change when the transition unfolds. References [1] Hughes, T. P., Linares, C., Dakos, V., van de Leemput, I. a, & van Nes, E. H. (2013). Living dangerously on borrowed time during slow, unrecognized regime shifts. Trends in ecology & evolution, 28(3), 149-55. [2] Karssenberg, D., & Bierkens, M. F. P. (2012). Early-warning signals (potentially) reduce uncertainty in forecasted timing of critical shifts. Ecosphere, 3(2).

Precision Muonium Spectroscopy

NASA Astrophysics Data System (ADS)

Jungmann, Klaus P.

2016-09-01

The muonium atom is the purely leptonic bound state of a positive muon and an electron. It has a lifetime of 2.2 µs. The absence of any known internal structure provides for precision experiments to test fundamental physics theories and to determine accurate values of fundamental constants. In particular ground state hyperfine structure transitions can be measured by microwave spectroscopy to deliver the muon magnetic moment. The frequency of the 1s-2s transition in the hydrogen-like atom can be determined with laser spectroscopy to obtain the muon mass. With such measurements fundamental physical interactions, in particular quantum electrodynamics, can also be tested at highest precision. The results are important input parameters for experiments on the muon magnetic anomaly. The simplicity of the atom enables further precise experiments, such as a search for muonium-antimuonium conversion for testing charged lepton number conservation and searches for possible antigravity of muons and dark matter.

Proximity-induced magnetism in transition-metal substituted graphene

PubMed Central

Crook, Charles B.; Constantin, Costel; Ahmed, Towfiq; Zhu, Jian-Xin; Balatsky, Alexander V.; Haraldsen, Jason T.

2015-01-01

We investigate the interactions between two identical magnetic impurities substituted into a graphene superlattice. Using a first-principles approach, we calculate the electronic and magnetic properties for transition-metal substituted graphene systems with varying spatial separation. These calculations are compared for three different magnetic impurities, manganese, chromium, and vanadium. We determine the electronic band structure, density of states, and Millikan populations (magnetic moment) for each atom, as well as calculate the exchange parameter between the two magnetic atoms as a function of spatial separation. We find that the presence of magnetic impurities establishes a distinct magnetic moment in the graphene lattice, where the interactions are highly dependent on the spatial and magnetic characteristic between the magnetic and carbon atoms, which leads to either ferromagnetic or antiferromagnetic behavior. Furthermore, through an analysis of the calculated exchange energies and partial density of states, it is determined that interactions between the magnetic atoms can be classified as an RKKY interaction. PMID:26235646

Theoretical study of some nitrososulfamide compounds with antitumor activity.

PubMed

Djameleddine, Khatmi; Soumeya, Seridi; Fatiha, Madi

2004-09-30

The lowest-energy conformations of four 2-chloroethylnitrososulfamides were determined using the MM+ molecular mechanics method as implemented in Hyperchem 6.0. Some of the calculated structural parameters, angles and bonds lengths were compared with the crystal structure data of N-nitroso-N-(2-chloroethyl)-N'-sulfamoyl- proline. Using MM+, AM1 and PM3 the anti conformation was predicted to be more stable than the syn conformation in each of these compounds. With these methods we found that the relative energy of the transition state (TS) was considerably higher, but with the ab initio method using RHF with minimal basic function STO-3G we found that the syn conformation is predicted to be slightly more stable. The determination of some atomic charges of a selection of atoms on the syn, anti and TS structures of the various compounds provided some details about the nature of the transition state.

Efficient determination of the Markovian time-evolution towards a steady-state of a complex open quantum system

NASA Astrophysics Data System (ADS)

Jonsson, Thorsteinn H.; Manolescu, Andrei; Goan, Hsi-Sheng; Abdullah, Nzar Rauf; Sitek, Anna; Tang, Chi-Shung; Gudmundsson, Vidar

2017-11-01

Master equations are commonly used to describe time evolution of open systems. We introduce a general computationally efficient method for calculating a Markovian solution of the Nakajima-Zwanzig generalized master equation. We do so for a time-dependent transport of interacting electrons through a complex nano scale system in a photon cavity. The central system, described by 120 many-body states in a Fock space, is weakly coupled to the external leads. The efficiency of the approach allows us to place the bias window defined by the external leads high into the many-body spectrum of the cavity photon-dressed states of the central system revealing a cascade of intermediate transitions as the system relaxes to a steady state. The very diverse relaxation times present in the open system, reflecting radiative or non-radiative transitions, require information about the time evolution through many orders of magnitude. In our approach, the generalized master equation is mapped from a many-body Fock space of states to a Liouville space of transitions. We show that this results in a linear equation which is solved exactly through an eigenvalue analysis, which supplies information on the steady state and the time evolution of the system.

Confinement effects on glass transition temperature, transition breadth, and expansivity: comparison of ellipsometry and fluorescence measurements on polystyrene films.

PubMed

Kim, S; Hewlett, S A; Roth, C B; Torkelson, J M

2009-09-01

Using ellipsometry, we characterized the nanoconfinement effect on the glass transition temperature (T (g)of supported polystyrene (PS) films employing two methods: the intersection of fits to the temperature (Tdependences of rubbery- and glassy-state thicknesses, and the transition mid-point between rubbery- and glassy-state expansivities. The results demonstrate a strong effect of thickness: T(g) (bulk) - T(g)(23 nm) = 10 degrees C. The T -range needed for accurate measurement increases significantly with decreasing thickness, an effect that arises from the broadening of the transition with confinement and a region below T (g) where expansivity slowly decreases with decreasing T . As determined from expansivities, the T (g) breadth triples in going from bulk films to a 21-nm-thick film; this broadening of the transition may be a more dramatic effect of confinement than the T (g) reduction itself. In contrast, there is little effect of confinement on the rubbery- and glassy-state expansivities. Compared with ellipsometry, T (g) 's from fluorescence agree well in bulk films but yield lower values in nanoconfined films: T (g)(bulk) - T (g)(23 nm) = 15( degrees ) C via fluorescence. This small difference in the T (g) confinement effect reflects differences in how fluorescence and ellipsometry report "average T (g) " with confinement. With decreasing nanoscale thickness, fluorescence may slightly overweight the contribution of the free-surface layer while ellipsometry may evenly weight or underweight its contribution.

Confinement effects on glass transition temperature, transition breadth, and expansivity: Comparison of ellipsometry and fluorescence measurements on polystyrene films

NASA Astrophysics Data System (ADS)

Kim, S.; Hewlett, S. A.; Roth, C. B.; Torkelson, J. M.

2009-09-01

Using ellipsometry, we characterized the nanoconfinement effect on the glass transition temperature (T gof supported polystyrene (PS) films employing two methods: the intersection of fits to the temperature (Tdependences of rubbery- and glassy-state thicknesses, and the transition mid-point between rubbery- and glassy-state expansivities. The results demonstrate a strong effect of thickness: ensuremath Tg(bulk)-Tg(23{ nm})= 10 circ C. The T -range needed for accurate measurement increases significantly with decreasing thickness, an effect that arises from the broadening of the transition with confinement and a region below T g where expansivity slowly decreases with decreasing T . As determined from expansivities, the T g breadth triples in going from bulk films to a 21-nm-thick film; this broadening of the transition may be a more dramatic effect of confinement than the T g reduction itself. In contrast, there is little effect of confinement on the rubbery- and glassy-state expansivities. Compared with ellipsometry, T g ’s from fluorescence agree well in bulk films but yield lower values in nanoconfined films: T g(bulk) - T g(23 nm) = 15° C via fluorescence. This small difference in the T g confinement effect reflects differences in how fluorescence and ellipsometry report “average T g ” with confinement. With decreasing nanoscale thickness, fluorescence may slightly overweight the contribution of the free-surface layer while ellipsometry may evenly weight or underweight its contribution. in here

An Ab Initio Study of the Low-Lying Doublet States of AgO and AgS

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.

1990-01-01

Spectroscopic constants (D(sub o), r(sub e), mu(sub e), T(sub e)) are determined for the doublet states of AgO and AgS below approx. = 30000/cm. Large valence basis sets are employed in conjunction with relativistic effective core potentials (RECPs). Electron correlation is included using the modified coupled-pair functional (MCPF) and multireference configuration interaction (MRCI) methods. The A(sup 2)Sigma(sup +) - X(sup 2)Pi band system is found to occur in the near infrared (approx. = 9000/cm) and to be relatively weak with a radiative lifetime of 900 microns for A(sup 2)Sigma(sup +) (upsilon = 0). The weakly bound C(sup 2)Pi state (our notation), the upper state of the blue system, is found to require high levels of theoretical treatment to determine a quantitatively accurate potential. The red system is assigned as a transition from the C(sup 2)Pi state to the previously unobserved A(sup 2)Sigma(sup +) state. Several additional transitions are identified that should be detectable experimentally. A more limited study is performed for the vertical excitation spectrum of AgS. In addition, a detailed all-electron study of the X(sup 2)Pi and A(sup 2)Sigma(sup +) states of AgO is carried out using large atomic natural orbital (ANO) basis sets. Our best calculated D(sub o) value for AgO is significantly less than the experimental value, which suggests that there may be some systematic error in the experimental determination.

How Cinchona Alkaloid-Derived Primary Amines Control Asymmetric Electrophilic Fluorination of Cyclic Ketones

PubMed Central

2015-01-01

The origin of selectivity in the α-fluorination of cyclic ketones catalyzed by cinchona alkaloid-derived primary amines is determined with density functional calculations. The chair preference of a seven-membered ring at the fluorine transfer transition state is key in determining the sense and level of enantiofacial selectivity. PMID:24967514

The ν8 band of C2HD3 by high-resolution synchrotron FTIR spectroscopy: Coriolis interactions between the v8 = 1 and v6 = 1 states

NASA Astrophysics Data System (ADS)

Ng, L. L.; Tan, T. L.; Akasyah, Luqman; Wong, Andy; Appadoo, Dominique R. T.; McNaughton, Don

2017-10-01

The synchrotron Fourier transform infrared (FTIR) spectrum of the ν8 band of ethylene-d3 (C2HD3) was measured at an unapodized resolution of 0.00096 cm-1 from 830 to 1010 cm-1. Rovibrational constants up to five quartic terms were derived with improved precision for the v8 = 1 state through the fitting of 1566 unperturbed infrared transitions using the Watson's A-reduced Hamiltonian in the Ir representation with a root-mean-square (rms) deviation of 0.00044 cm-1. For the first time, 446 perturbed IR transitions of the ν8 band were fitted together with the 1566 unperturbed infrared transitions to obtain the a- and b-Coriolis resonance parameters from its interaction with the v6 = 1 state, with an rms deviation of 0.00039 cm-1. The IR lines of the ν6 band were too weak for detection. Three rotational constants, a quartic constant and band center of the v6 = 1 state were also derived for the first time in this work. Ground state rovibrational constants of C2HD3 up to five quartic constants were also derived from a fit of 906 ground state combination differences with an rms deviation of 0.00030 cm-1 from infrared transitions of the present analysis. The ground state rotational constants are in close agreement with theoretically calculated values using the cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels of theory. Alpha constants determined from the rotational constants of the v8 = 1 state derived from the perturbed IR fit compared favourably with those from anharmonic calculations.

Crossflow Stability and Transition Experiments in a Swept-Wing Flow. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Dagenhart, John Ray

1992-01-01

An experimental examination of crossflow instability and transition on a 45 degree swept wing is conducted in the Arizona State University Unsteady Wind Tunnel. The stationary-vortex pattern and transition location are visualized using both sublimating-chemical and liquid-crystal coatings. Extensive hot-wire measurements are conducted at several measurement stations across a single vortex track. The mean and travelling-wave disturbances are measured simultaneously. Stationary-crossflow disturbance profiles are determined by subtracting either a reference or a span-averaged velocity profile from the mean-velocity data. Mean, stationary-crossflow, and travelling-wave velocity data are presented as local boundary-layer profiles and as contour plots across a single stationary-crossflow vortex track. Disturbance-mode profiles and growth rates are determined. The experimental data are compared to predictions from linear stability theory.

The fine-structure intervals of (N-14)+ by far-infrared laser magnetic resonance

NASA Technical Reports Server (NTRS)

Brown, John M.; Varberg, Thomas D.; Evenson, Kenneth M.; Cooksy, Andrew L.

1994-01-01

The far-infrared laser magnetic resonance spectra associated with both fine-structure transitions in (N-14)+ in its ground P-3 state have been recorded. This is the first laboratory observation of the J = 1 left arrow 0 transition and its frequency has been determined two orders of magnitude more accurately than previously. The remeasurement of the J = 2 left arrow 1 spectrum revealed a small error in the previous laboratory measurements. The fine-structure splittings (free of hyperfine interactions) determined in this work are (delta)E(sub 10) = 1461.13190 (61) GHz, (delta)E(sub 21) = 2459.38006 (37) GHz. Zero-field transition frequencies which include the effects of hyperfine structure have also been calculated. Refined values for the hyperfine constants and the g(sub J) factors have been obtained.

Reacting gas mixtures in the state-to-state approach: The chemical reaction rates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kustova, Elena V.; Kremer, Gilberto M.

2014-12-09

In this work chemically reacting mixtures of viscous flows are analyzed within the framework of Boltzmann equation. By applying a modified Chapman-Enskog method to the system of Boltzmann equations general expressions for the rates of chemical reactions and vibrational energy transitions are determined as functions of two thermodynamic forces: the velocity divergence and the affinity. As an application chemically reacting mixtures of N{sub 2} across a shock wave are studied, where the first lowest vibrational states are taken into account. Here we consider only the contributions from the first four single quantum vibrational-translational energy transitions. It is shown that themore » contribution to the chemical reaction rate related to the affinity is much larger than that of the velocity divergence.« less

Single-photon cesium Rydberg excitation spectroscopy using 318.6-nm UV laser and room-temperature vapor cell.

PubMed

Wang, Jieying; Bai, Jiandong; He, Jun; Wang, Junmin

2017-09-18

We demonstrate a single-photon Rydberg excitation spectroscopy of cesium (Cs) atoms in a room-temperature vapor cell. Cs atoms are excited directly from 6S 1/2 ground state to nP 3/2 (n = 70 - 100) Rydberg states with a 318.6 nm ultraviolet (UV) laser, and Rydberg excitation spectra are obtained by transmission enhancement of a probe beam resonant to Cs 6S 1/2 , F = 4 - 6P 3/2 , F' = 5 transition as partial population on F = 4 ground state are transferred to Rydberg state. Analysis reveals that the observed spectra are velocity-selective spectroscopy of Rydberg state, from which the amplitude and linewidth influenced by lasers' Rabi frequency have been investigated. Fitting to energies of Cs nP 3/2 (n = 70 -100) states, the determined quantum defect is 3.56671(42). The demodulated spectra can also be employed as frequency references to stabilize the UV laser frequency to specific Cs Rydberg transition.

Predict the glass transition temperature of glycerol-water binary cryoprotectant by molecular dynamic simulation.

PubMed

Li, Dai-Xi; Liu, Bao-Lin; Liu, Yi-shu; Chen, Cheng-lung

2008-04-01

Vitrification is proposed to be the best way for the cryopreservation of organs. The glass transition temperature (T(g)) of vitrification solutions is a critical parameter of fundamental importance for cryopreservation by vitrification. The instruments that can detect the thermodynamic, mechanical and dielectric changes of a substance may be used to determine the glass transition temperature. T(g) is usually measured by using differential scanning calorimetry (DSC). In this study, the T(g) of the glycerol-aqueous solution (60%, wt/%) was determined by isothermal-isobaric molecular dynamic simulation (NPT-MD). The software package Discover in Material Studio with the Polymer Consortium Force Field (PCFF) was used for the simulation. The state parameters of heat capacity at constant pressure (C(p)), density (rho), amorphous cell volume (V(cell)) and specific volume (V(specific)) and radial distribution function (rdf) were obtained by NPT-MD in the temperature range of 90-270K. These parameters showed a discontinuity at a specific temperature in the plot of state parameter versus temperature. The temperature at the discontinuity is taken as the simulated T(g) value for glycerol-water binary solution. The T(g) values determined by simulation method were compared with the values in the literatures. The simulation values of T(g) (160.06-167.51K) agree well with the DSC results (163.60-167.10K) and the DMA results (159.00K). We drew the conclusion that molecular dynamic simulation (MDS) is a potential method for investigating the glass transition temperature (T(g)) of glycerol-water binary cryoprotectants and may be used for other vitrification solutions.

Probing quantum frustrated systems via factorization of the ground state.

PubMed

Giampaolo, Salvatore M; Adesso, Gerardo; Illuminati, Fabrizio

2010-05-21

The existence of definite orders in frustrated quantum systems is related rigorously to the occurrence of fully factorized ground states below a threshold value of the frustration. Ground-state separability thus provides a natural measure of frustration: strongly frustrated systems are those that cannot accommodate for classical-like solutions. The exact form of the factorized ground states and the critical frustration are determined for various classes of nonexactly solvable spin models with different spatial ranges of the interactions. For weak frustration, the existence of disentangling transitions determines the range of applicability of mean-field descriptions in biological and physical problems such as stochastic gene expression and the stability of long-period modulated structures.

Electronic spectrum of jet cooled SiCN

NASA Astrophysics Data System (ADS)

Fukushima, Masaru; Ishiwata, Takashi

2016-09-01

We have generated SiCN in a supersonic free expansion, and measured the laser induced fluorescence (LIF) spectrum. Prior to the experiments, ab initio calculations were carried out to obtain the information necessary for searching for the LIF signals. In addition to the X ˜ 2Π state, the optimized structures of three excited states, 2Δ, 2Σ+, and 2Σ-, have been obtained. Guided by the predictions, the LIF excitation spectrum of SiCN was observed in the UV region. The rotational structure of the 00 0 band with the origin, 29 261.639 cm-1, indicated that the electronic transition is A ˜ 2Δ- X ˜ 2Π. The spin-orbit (SO) constants of the X ˜ 2Π and A ˜ 2Δ states were determined to be 140.824 and 4.944 cm-1, respectively. In the A ˜ 2Δ state, the Fermi resonance between the (0, 20, 0) 2Δ and (0, 00, 1) 2Δ vibronic levels was identified. The molecular constants of the X ˜ 2Π state were determined through the simultaneous analysis of the combination differences derived from the present LIF data with the previously reported rotational transitions. The spectroscopic parameters of the A ˜ 2Δ state were also obtained from the analysis where the constants of the X ˜ 2Π state, derived above, were fixed at those values.

Phase Transitions of MgO Along the Hugoniot (Invited)

NASA Astrophysics Data System (ADS)

Root, S.; Shulenburger, L.; Lemke, R. W.; Cochrane, K. R.; Mattsson, T. R.

2013-12-01

The formation of terrestrial planets and planetary structure has become of great interest because of recent exoplanet discoveries of super earths. MgO is a major constituent of Earth's mantle, the rocky cores of gas giants such as Jupiter, and likely constitutes the interiors of many exoplanets. The high pressure - high temperature behavior of MgO directly affects equation of state models for planetary structure and formation. In this work, we examine single crystal MgO under shock compression utilizing experimental and density functional theory (DFT) methods to determine phase transformations along the Hugoniot. We perform plate impact experiments using Sandia's Z - facility on MgO up to 11.6 Mbar. The plate impact experiments generate highly accurate Hugoniot state data. The experimental results show the B1 - B2 solid - solid phase transition occurs near 4 Mbar on the Hugoniot. The solid - liquid transition is determined to be near 7 Mbar with a large region of B2-liquid coexistence. Using DFT methods, we also determine melt along the B1 and B2 solid phase boundaries as well as along the Hugoniot. The combined experimental and DFT results have determined the phase boundaries along the Hugoniot, which can be implemented into new planetary and EOS models. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Securities Administration under Contract No. DE-AC04-94AL85000.

Ab initio calculations of potential energy curves of Hg/sub 2/ and TlHg

DOE Office of Scientific and Technical Information (OSTI.GOV)

Celestino, K.C.; Ermler, W.C.

1984-08-15

Potential energy curves for electronic states of Hg/sub 2/ and TlHg are presented and analyzed. They are derived using large scale configuration interaction procedures for the valence electrons, with the core electrons represented by ab initio relativistic effective potentials. The effect of spin-orbit coupling are investigated for the low-lying excimer states. It is determined that neither system possesses strongly bound electronic states for which transitions to the repulsive ground states are optically allowed.

Critical threshold behavior for steady-state internal transport barriers in burning plasmas.

PubMed

García, J; Giruzzi, G; Artaud, J F; Basiuk, V; Decker, J; Imbeaux, F; Peysson, Y; Schneider, M

2008-06-27

Burning tokamak plasmas with internal transport barriers are investigated by means of integrated modeling simulations. The barrier sustainment in steady state, differently from the barrier formation process, is found to be characterized by a critical behavior, and the critical number of the phase transition is determined. Beyond a power threshold, alignment of self-generated and noninductively driven currents occurs and steady state becomes possible. This concept is applied to simulate a steady-state scenario within the specifications of the International Thermonuclear Experimental Reactor.

Location identification of closed crack based on Duffing oscillator transient transition

NASA Astrophysics Data System (ADS)

Liu, Xiaofeng; Bo, Lin; Liu, Yaolu; Zhao, Youxuan; Zhang, Jun; Deng, Mingxi; Hu, Ning

2018-02-01

The existence of a closed micro-crack in plates can be detected by using the nonlinear harmonic characteristics of the Lamb wave. However, its location identification is difficult. By considering the transient nonlinear Lamb under the noise interference, we proposed a location identification method for the closed crack based on the quantitative measurement of Duffing oscillator transient transfer in the phase space. The sliding short-time window was used to create a window truncation of to-be-detected signal. And then, the periodic extension processing for transient nonlinear Lamb wave was performed to ensure that the Duffing oscillator has adequate response time to reach a steady state. The transient autocorrelation method was used to reduce the occurrence of missed harmonic detection due to the random variable phase of nonlinear Lamb wave. Moreover, to overcome the deficiency in the quantitative analysis of Duffing system state by phase trajectory diagram and eliminate the misjudgment caused by harmonic frequency component contained in broadband noise, logic operation method of oscillator state transition function based on circular zone partition was adopted to establish the mapping relation between the oscillator transition state and the nonlinear harmonic time domain information. Final state transition discriminant function of Duffing oscillator was used as basis for identifying the reflected and transmitted harmonics from the crack. Chirplet time-frequency analysis was conducted to identify the mode of generated harmonics and determine the propagation speed. Through these steps, accurate position identification of the closed crack was achieved.

Binding Energy and Enzymatic Catalysis.

ERIC Educational Resources Information Center

Hansen, David E.; Raines, Ronald T.

1990-01-01

Discussed is the fundamental role that the favorable free energy of binding of the rate-determining transition state plays in catalysis. The principle that all of the catalytic factors discussed are realized by the use of this binding energy is reviewed. (CW)

Site-directed mutagenesis reveals transition-state stabilization as a general catalytic mechanism for aminoacyl-tRNA synthetases.

PubMed

Borgford, T J; Gray, T E; Brand, N J; Fersht, A R

1987-11-17

Some aminoacyl-tRNA synthetases of almost negligible homology do have a small region of similarity around four-residue sequence His-Ile(or Leu or Met)-Gly-His(or Asn), the HIGH sequence. The first histidine in this sequence in the tyrosyl-tRNA synthetase, His-45, has been shown to form part of a binding site for the gamma-phosphate of ATP in the transition state for the reaction as does Thr-40. Residue His-56 in the valyl-tRNA synthetase begins a HIGH sequence, and there is a threonine at position 52, one position closer to the histidine than in the tyrosyl-tRNA synthetase. The mutants Thr----Ala-52 and His----Asn-56 have been made and their complete free energy profiles for the formation of valyl adenylate determined. Difference energy diagrams have been constructed by comparison with the reaction of wild-type enzyme. The difference energy profiles are very similar to those for the mutants Thr----Ala-40 and His----Asn-45 of the tyrosyl-tRNA synthetase. Thr-52 and His-56 of the valyl-tRNA synthetase contribute little binding energy to valine, ATP, and Val-AMP. Instead, the wild-type enzyme binds the transition state and pyrophosphate some 6 kcal/mol more tightly than do the mutants. Preferential transition-state stabilization is thus an important component of catalysis by the valyl-tRNA synthetase. Further, by analogy to the tyrosyl-tRNA synthetase, the valyl-tRNA synthetase has a binding site for the gamma-phosphate of ATP in the transition state, and this is likely to be a general feature of aminoacyl-tRNA synthetases that have a HIGH region.

The fluorescence intensities ratio is not a reliable parameter for evaluation of protein unfolding transitions.

PubMed

Žoldák, Gabriel; Jancura, Daniel; Sedlák, Erik

2017-06-01

Monitoring the fluorescence of proteins, particularly the fluorescence of intrinsic tryptophan residues, is a popular method often used in the analysis of unfolding transitions (induced by temperature, chemical denaturant, and pH) in proteins. The tryptophan fluorescence provides several suitable parameters, such as steady-state fluorescence intensity, apparent quantum yield, mean fluorescence lifetime, position of emission maximum that are often utilized for the observation of the conformational/unfolding transitions of proteins. In addition, the fluorescence intensities ratio at different wavelengths (usually at 330 nm and 350 nm) is becoming an increasingly popular parameter for the evaluation of thermal transitions. We show that, under certain conditions, the use of this parameter for the analysis of unfolding transitions leads to the incorrect determination of thermodynamic parameters characterizing unfolding transitions in proteins (e.g., melting temperature) and, hence, can compromise the hit identification during high-throughput drug screening campaigns. © 2017 The Protein Society.

Metal-Insulator Transition Revisited for Cold Atoms in Non-Abelian Gauge Potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Satija, Indubala I.; National Institute of Standards and Technology, Gaithersburg, Maryland 20899; Dakin, Daniel C.

2006-11-24

We discuss the possibility of realizing metal-insulator transitions with ultracold atoms in two-dimensional optical lattices in the presence of artificial gauge potentials. For Abelian gauges, such transitions occur when the magnetic flux penetrating the lattice plaquette is an irrational multiple of the magnetic flux quantum. Here we present the first study of these transitions for non-Abelian U(2) gauge fields. In contrast to the Abelian case, the spectrum and localization transition in the non-Abelian case is strongly influenced by atomic momenta. In addition to determining the localization boundary, the momentum fragments the spectrum. Other key characteristics of the non-Abelian case includemore » the absence of localization for certain states and satellite fringes around the Bragg peaks in the momentum distribution and an interesting possibility that the transition can be tuned by the atomic momenta.« less

Hyperfine interaction constants of 14NO2 in 14 500-16 800 cm-1 energy region

NASA Astrophysics Data System (ADS)

Tada, Kohei; Hirata, Michihiro; Kasahara, Shunji

2017-10-01

We observed hyperfine-resolved high-resolution fluorescence excitation spectra of k = 0, N = 1 ← 0 transitions in 82 vibronic bands of the à 2B2 ← X ˜ 2A1 system of 14NO2 in the 14 500-16 800 cm-1 region by crossing a jet-cooled molecular beam and a single-mode dye laser beam at right angles. We determined hyperfine interaction constants of the lower and upper states for all the observed vibronic bands based on the analysis of the hyperfine structures of k = 0, N = 1 ← 0 transitions. Most of the determined Fermi contact interaction constants were found to be distributed in 0.0013-0.0038 cm-1, which are intermediate in magnitude between those in lower and higher energy region reported by other groups. A sharp decreasing of the Fermi contact interaction constant was found in 16 200-16 600 cm-1, and it may be caused by the interaction with the dark C ˜ 2A2 state. The hyperfine interaction constants are powerful clues to obtain reliable vibronic assignment. We tentatively assigned vibronic bands located at 14 836 cm-1, 15 586 cm-1, and 16 322 cm-1 as the transitions to the intrinsic (0,7,0), (0,8,0), and (0,9,0) vibrational levels of the à 2B2 state, respectively.

Determination of magic wavelengths for the 7 s 1/2 2S -7 p 3/2, 1/2 2P transitions in Fr

NASA Astrophysics Data System (ADS)

Singh, Sukhjit; Sahoo, B. K.; Arora, Bindiya

2016-08-01

Magic wavelengths (λmagic) for the 7 S1 /2-7 P1 /2 ,3 /2 transitions (D lines) in Fr were reported by Dammalapati et al. [U. Dammalapati, K. Harada, and Y. Sakemi, Phys. Rev. A 93, 043407 (2016), 10.1103/PhysRevA.93.043407]. These λmagic were determined by plotting dynamic polarizabilities (α ) of the involved states with the above transitions against a desired range of wavelengths. Electric dipole (E1) matrix elements listed in [J. E. Sansonetti, J. Phys. Chem. Ref. Data 36, 497 (2007), 10.1063/1.2719251], from the measured lifetimes of the 7 P1 /2 ,3 /2 states and from the calculations considering core-polarization effects in the relativistic Hartree-Fock (HFR) method, were used to determine α . However, contributions from core correlation effects and from the E1 matrix elements of the 7 P -7 S , 7 P -8 S , and 7 P -6 D transitions to α of the 7 P states were ignored. In this work, we demonstrate importance of these contributions and improve accuracies of α further by replacing the E1 matrix elements taken from the HFR method by the values obtained employing relativistic coupled-cluster theory. Our static α are found to be in excellent agreement with the other available theoretical results, whereas substituting the E1 matrix elements used by Dammalapati et al. gives very small α values for the 7 P states. Owing to this, we find disagreement in λmagic reported by Dammalapati et al. for linearly polarized light, especially at wavelengths close to the D lines and in the infrared region. As a consequence, a λmagic reported at 797.75 nm which was seen supporting a blue detuned trap in their work is now estimated at 771.03 nm and is supporting a red detuned trap. Also, none of our results match with the earlier results for circularly polarized light. Moreover, our static values of α will be very useful for guiding experiments to carry out their measurements.

Ground-state and pairing-vibrational bands with equal quadrupole collectivity in 124Xe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Radich, A. J.; Garrett, P. E.; Allmond, J. M.

The nuclear structure of 124Xe has been investigated via measurements of the β +/EC decay of 124Cs with the 8π γ-ray spectrometer at the TRIUMF-ISAC facility. The data collected have enabled branching ratio measurements of weak, low-energy transitions from highly excited states, and the 2 + → 0 + in-band transitions have been observed. Combining these results with those from a previous Coulomb excitation study,more » $$B(E2; 2^+_3 → 0^+_2)$$ = 78(13) W.u. and $$B(E2; 2^+_4 → 0^+_3)$$ = 53(12) W.u. were determined. The $$0^+_3$$ state, in particular, is interpreted as the main fragment of the proton-pairing vibrational band identified in a previous 122Te( 3He,n) 124Xe measurement, and has quadrupole collectivity equal to, within uncertainty, that of the ground-state band.« less

Ground-state and pairing-vibrational bands with equal quadrupole collectivity in 124Xe

DOE PAGES

Radich, A. J.; Garrett, P. E.; Allmond, J. M.; ...

2015-04-01

The nuclear structure of 124Xe has been investigated via measurements of the β +/EC decay of 124Cs with the 8π γ-ray spectrometer at the TRIUMF-ISAC facility. The data collected have enabled branching ratio measurements of weak, low-energy transitions from highly excited states, and the 2 + → 0 + in-band transitions have been observed. Combining these results with those from a previous Coulomb excitation study,more » $$B(E2; 2^+_3 → 0^+_2)$$ = 78(13) W.u. and $$B(E2; 2^+_4 → 0^+_3)$$ = 53(12) W.u. were determined. The $$0^+_3$$ state, in particular, is interpreted as the main fragment of the proton-pairing vibrational band identified in a previous 122Te( 3He,n) 124Xe measurement, and has quadrupole collectivity equal to, within uncertainty, that of the ground-state band.« less

Theoretical evaluation of the radiative lifetimes of LiCs and NaCs in the A1Σ+ state

NASA Astrophysics Data System (ADS)

Mabrouk, N.; Berriche, H.

2017-08-01

Calculations of the adiabatic potential energy curves and the transition dipole moments between the ground (A1Σ+) and the first excited (A1Σ+) states have been determined for the LiCs and NaCs molecules. The calculations are performed using an ab initio approach based on non-empirical pseudopotentials for Cs+, Li+ and Na+ cores, parameterized l-dependent polarization potentials and full configuration interaction calculations. The potential energy curves and the transition dipole moment are used to estimate the radiative lifetimes of the vibrational levels of the A+Σ+ state using the Franck-Condon (FC) approximation and the approximate sum rule method. The radiative lifetimes associated with the A+Σ+ state are presented here for the first time. These data can help experimentalists to optimize photoassociative formation of ultracold molecules and their longevity in a trap or in an optical lattice.

Proposal for the determination of nuclear masses by high-precision spectroscopy of Rydberg states

NASA Astrophysics Data System (ADS)

Wundt, B. J.; Jentschura, U. D.

2010-06-01

The theoretical treatment of Rydberg states in one-electron ions is facilitated by the virtual absence of the nuclear-size correction, and fundamental constants like the Rydberg constant may be in the reach of planned high-precision spectroscopic experiments. The dominant nuclear effect that shifts transition energies among Rydberg states therefore is due to the nuclear mass. As a consequence, spectroscopic measurements of Rydberg transitions can be used in order to precisely deduce nuclear masses. A possible application of this approach to hydrogen and deuterium, and hydrogen-like lithium and carbon is explored in detail. In order to complete the analysis, numerical and analytic calculations of the quantum electrodynamic self-energy remainder function for states with principal quantum number n = 5, ..., 8 and with angular momentum ell = n - 1 and ell = n - 2 are described \\big(j = \\ell \\pm {\\textstyle {\\frac{1}{2}}}\\big).

A methodology for stochastic analysis of share prices as Markov chains with finite states.

PubMed

Mettle, Felix Okoe; Quaye, Enoch Nii Boi; Laryea, Ravenhill Adjetey

2014-01-01

Price volatilities make stock investments risky, leaving investors in critical position when uncertain decision is made. To improve investor evaluation confidence on exchange markets, while not using time series methodology, we specify equity price change as a stochastic process assumed to possess Markov dependency with respective state transition probabilities matrices following the identified state pace (i.e. decrease, stable or increase). We established that identified states communicate, and that the chains are aperiodic and ergodic thus possessing limiting distributions. We developed a methodology for determining expected mean return time for stock price increases and also establish criteria for improving investment decision based on highest transition probabilities, lowest mean return time and highest limiting distributions. We further developed an R algorithm for running the methodology introduced. The established methodology is applied to selected equities from Ghana Stock Exchange weekly trading data.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sinitsyn, Nikolai A.

In this paper, I identify a nontrivial four-state Landau-Zener model for which transition probabilities between any pair of diabatic states can be determined analytically and exactly. The model describes an experimentally accessible system of two interacting qubits, such as a localized state in a Dirac material with both valley and spin degrees of freedom or a singly charged quantum dot (QD) molecule with spin orbit coupling. Application of the linearly time-dependent magnetic field induces a sequence of quantum level crossings with possibility of interference of different trajectories in a semiclassical picture. I argue that this system satisfies the criteria ofmore » integrability in the multistate Landau-Zener theory, which allows one to derive explicit exact analytical expressions for the transition probability matrix. Finally, I also argue that this model is likely a special case of a larger class of solvable systems, and present a six-state generalization as an example.« less

Excitonic linewidth and coherence lifetime in monolayer transition metal dichalcogenides

DOE PAGES

Selig, Malte; Berghäuser, Gunnar; Raja, Archana; ...

2016-11-07

Atomically thin transition metal dichalcogenides are direct-gap semiconductors with strong light–matter and Coulomb interactions. The latter accounts for tightly bound excitons, which dominate their optical properties. Besides the optically accessible bright excitons, these systems exhibit a variety of dark excitonic states. They are not visible in the optical spectra, but can strongly influence the coherence lifetime and the linewidth of the emission from bright exciton states. We investigate the microscopic origin of the excitonic coherence lifetime in two representative materials (WS 2 and MoSe 2) through a study combining microscopic theory with spectroscopic measurements. We also show that the excitonicmore » coherence lifetime is determined by phonon-induced intravalley scattering and intervalley scattering into dark excitonic states. Particularly, we identify exciton relaxation processes involving phonon emission into lower-lying dark states that are operative at all temperatures, in WS 2.« less

The Processing of High Temperature Ceramic Superconducting Devices. Volume 1.

DTIC Science & Technology

1992-01-31

assuming frequency squared dependence) for ease of comparison with other measurements. At the low power levels the surface resistance is I 200 micro ...transition temperature is 106K, where the measured resistivity becomes zero. The noimal state resistivity at the transition temperature, 100 micro -ohms...our films at temperatures down t o 4K. A four-point measurement is used, and the criterion of 1 micro -volt per millimeter is usedI to determine

Molecules in high spin states: The millimeter and submillimeter spectrum of the MnS radical (X 6Sigma+)

NASA Astrophysics Data System (ADS)

Thompsen, J. M.; Brewster, M. A.; Ziurys, L. M.

2002-06-01

The pure rotational spectrum of MnS (v=0) in its X 6Sigma+ ground state has been recorded using millimeter and submillimeter direct absorption techniques in the range 160-502 GHz. MnS was synthesized in the gas phase by the reaction of manganese vapor and CS2 in a high-temperature Broida-type oven. Fourteen rotational transitions for this radical were measured, each consisting of six fine-structure components. In the lower rotational lines, hyperfine structure, arising from the 55Mn nuclear spin of 5/2, was also resolved in each spin component. These data were analyzed using a case (b) Hamiltonian, and rotational, fine structure, and hyperfine parameters determined for MnS. In the analysis, the third-order correction to the spin-rotation interaction, gammaS, and the fourth-order spin-spin coupling term, theta, were found necessary for an acceptable fit. The hyperfine constants determined suggest that MnS is more covalent than MnO, but more ionic than MnH. There additionally appears to be considerable sdsigma hybridization in molecular orbital formation for this molecule. Bond lengths of the 3d transition-metal sulfides were compared as well, and those of MnS, CuS, and TiS do not follow the trend of their oxide analogs. This result indicates that there are significant bonding differences between transition-metal sulfides and transition-metal oxides.

Stretch-collapse transition of polyelectrolyte brushes in a poor solvent

NASA Astrophysics Data System (ADS)

von Goeler, F.; Muthukumar, M.

1996-12-01

This paper describes the behavior of charged, polymer brushes in electrolyte solutions of varying solvent quality. The brush height, d, dependence on the chain length, L (=Nl, where l is the Kuhn length), the grafting density σ, and solvent conditions is determined. We consider a monomer-monomer potential consisting of three components: (1) a long-ranged, screened Coulombic component of strength v¯/l (l is the Kuhn length) and range κ-1; (2) a short-ranged, two-body component of strength w¯l; and (3) a short-ranged, three-body component of strength ūl3. In particular, we examine the transition from a stretched state to a collapsed state in a poor solvent (w¯<0) as the solvent quality is decreased. Using dimensional analysis, Monte Carlo methods, and a variational technique, a first order transition is observed as predicted by the scaling arguments of Ross et al. and Borisov et al. for high charge/grafting densities. Using a variational procedure, we derive an analytical expression for the brush size and determine, quantitatively, the critical conditions for a first order transition in terms of key dimensionless variables, vN5/2, κlN1/2, wN3/2, and uN2 (where v=2πσl2v¯, w=σl2w¯, and u=σ2l4ū).

Coherent manipulation of three-qubit states in a molecular single-ion magnet

NASA Astrophysics Data System (ADS)

Jenkins, M. D.; Duan, Y.; Diosdado, B.; García-Ripoll, J. J.; Gaita-Ariño, A.; Giménez-Saiz, C.; Alonso, P. J.; Coronado, E.; Luis, F.

2017-02-01

We study the quantum spin dynamics of nearly isotropic Gd3 + ions entrapped in polyoxometalate molecules and diluted in crystals of a diamagnetic Y3 + derivative. The full energy-level spectrum and the orientations of the magnetic anisotropy axes have been determined by means of continuous-wave electron paramagnetic resonance experiments, using X-band (9-10 GHz) cavities and on-chip superconducting waveguides and 1.5-GHz resonators. The results show that seven allowed transitions between the 2 S +1 spin states can be separately addressed. Spin coherence T2 and spin-lattice relaxation T1 rates have been measured for each of these transitions in properly oriented single crystals. The results suggest that quantum spin coherence is limited by residual dipolar interactions with neighbor electronic spins. Coherent Rabi oscillations have been observed for all transitions. The Rabi frequencies increase with microwave power and agree quantitatively with predictions based on the spin Hamiltonian of the molecular spin. We argue that the spin states of each Gd3 + ion can be mapped onto the states of three addressable qubits (or, alternatively, of a d =8 -level "qudit"), for which the seven allowed transitions form a universal set of operations. Within this scheme, one of the coherent oscillations observed experimentally provides an implementation of a controlled-controlled-NOT (or Toffoli) three-qubit gate.

High-resolution Fourier-transform infrared spectroscopy of the ν6 and Coriolis perturbation allowed ν10 modes of ketenimine.

PubMed

Bane, Michael K; Robertson, Evan G; Thompson, Christopher D; Appadoo, Dominique R T; McNaughton, Don

2011-12-14

High-resolution FTIR spectra of the short lived species ketenimine have been recorded in the region 700-1300 cm(-1) and over 1500 transitions of the ν(10) and ν(6) modes have been assigned. Effective rotational and centrifugal distortion parameters for the v(10) = 1 and v(6) = 1 (excluding K(a) = 5) states were determined by co-fitting transitions, and treating strong a- and c-axis Coriolis interactions between them. Other perturbations attributed to interactions with the v(8) = 2 and v(12) = 1 + v(8) = 1 dark-states were also observed and treated. The ν(10) transitions are predicted to be inherently very weak, but are enhanced by an intensity stealing effect with the highly IR active ν(6) mode. A mechanism for this intensity stealing in ketenimine is also detailed. © 2011 American Institute of Physics

Relaxor-ferroelectric crossover in (B i1 /2K1 /2)Ti O3 : Origin of the spontaneous phase transition and the effect of an applied external field

NASA Astrophysics Data System (ADS)

Hagiwara, Manabu; Ehara, Yoshitaka; Novak, Nikola; Khansur, Neamul H.; Ayrikyan, Azatuhi; Webber, Kyle G.; Fujihara, Shinobu

2017-07-01

The temperature evolution of polar order in an A -site complex perovskite (B i1 /2K1 /2)Ti O3 (BKT) has been investigated by measurements of dielectric permittivity, depolarization current, and stress-stain curves at elevated temperatures. Upon cooling from high temperatures, BKT first enters a relaxor state and then spontaneously transforms into a ferroelectric state. The analyses of temperature and frequency dependence of permittivity have revealed that polar nanoregions of the relaxor phase appear at temperatures higher than 560°C, and also that their freezing at 296°C triggers the spontaneous relaxor-ferroelectric transition. We discuss the key factors determining the development of long-range polar order in A -site complex perovskites through a comparison with the relaxor (B i1 /2N a1 /2)Ti O3 . We also show that application of biasing electric fields and compressive stresses to BKT favors its ferroelectric phase, resulting in a significant shift of the relaxor-ferroelectric transition temperature towards higher temperatures. Based on the obtained results, electric field-temperature and stress-temperature phase diagrams are firstly determined for BKT.

Chiral and deconfinement phase transition in the Hamiltonian approach to QCD in Coulomb gauge

NASA Astrophysics Data System (ADS)

Reinhardt, H.; Vastag, P.

2016-11-01

The chiral and deconfinement phase transitions are investigated within the variational Hamiltonian approach to QCD in Coulomb gauge. The temperature β-1 is introduced by compactifying a spatial dimension. Thereby the whole temperature dependence is encoded in the vacuum state on the spatial manifold R2×S1(β ) . The chiral quark condensate and the dual quark condensate (dressed Polyakov loop) are calculated as a function of the temperature. From their inflection points the pseudocritical temperatures for the chiral and deconfinement crossover transitions are determined. Using the zero-temperature quark and gluon propagators obtained within the variational approach as input, we find 170 and 198 MeV, respectively, for the chiral and deconfinement transition.

Kinetic isotope effect in malonaldehyde determined from path integral Monte Carlo simulations.

PubMed

Huang, Jing; Buchowiecki, Marcin; Nagy, Tibor; Vaníček, Jiří; Meuwly, Markus

2014-01-07

The primary H/D kinetic isotope effect on the intramolecular proton transfer in malonaldehyde is determined from quantum instanton path integral Monte Carlo simulations on a fully dimensional and validated potential energy surface for temperatures between 250 and 1500 K. Our calculations, based on thermodynamic integration with respect to the mass of the transferring particle, are significantly accelerated by the direct evaluation of the kinetic isotope effect instead of computing it as a ratio of two rate constants. At room temperature, the KIE from the present simulations is 5.2 ± 0.4. The KIE is found to vary considerably as a function of temperature and the low-T behaviour is dominated by the fact that the free energy derivative in the reactant state increases more rapidly than in the transition state. Detailed analysis of the various contributions to the quantum rate constant together with estimates for rates from conventional transition state theory and from periodic orbit theory suggest that the KIE in malonaldehyde is dominated by zero point energy effects and that tunneling plays a minor role at room temperature.

Quantifying the underlying landscape and paths of cancer

PubMed Central

Li, Chunhe; Wang, Jin

2014-01-01

Cancer is a disease regulated by the underlying gene networks. The emergence of normal and cancer states as well as the transformation between them can be thought of as a result of the gene network interactions and associated changes. We developed a global potential landscape and path framework to quantify cancer and associated processes. We constructed a cancer gene regulatory network based on the experimental evidences and uncovered the underlying landscape. The resulting tristable landscape characterizes important biological states: normal, cancer and apoptosis. The landscape topography in terms of barrier heights between stable state attractors quantifies the global stability of the cancer network system. We propose two mechanisms of cancerization: one is by the changes of landscape topography through the changes in regulation strengths of the gene networks. The other is by the fluctuations that help the system to go over the critical barrier at fixed landscape topography. The kinetic paths from least action principle quantify the transition processes among normal state, cancer state and apoptosis state. The kinetic rates provide the quantification of transition speeds among normal, cancer and apoptosis attractors. By the global sensitivity analysis of the gene network parameters on the landscape topography, we uncovered some key gene regulations determining the transitions between cancer and normal states. This can be used to guide the design of new anti-cancer tactics, through cocktail strategy of targeting multiple key regulation links simultaneously, for preventing cancer occurrence or transforming the early cancer state back to normal state. PMID:25232051

Magnetic dipole transitions of Bc and Bc* mesons in the relativistic independent quark model

NASA Astrophysics Data System (ADS)

Patnaik, Sonali; Dash, P. C.; Kar, Susmita; Patra, Sweta P.; Barik, N.

2017-12-01

We study M1-transitions involving mesons: Bc(1 s ), Bc*(1 s ), Bc(2 s ), Bc*(2 s ), Bc(3 s ), and Bc*(3 s ) in the relativistic independent quark (RIQ) model based on a flavor independent average potential in the scalar-vector harmonic form. The transition form factor for Bc*→Bcγ is found to have analytical continuation from spacelike to physical timelike region. Our predicted coupling constant gBc*Bc=0.34 GeV-1 and decay width Γ (Bc*→Bcγ )=23 eV agree with other model predictions. In view of possible observation of Bc and Bc* s-wave states at LHC and Z-factory and potential use of theoretical estimate on M1-transitions, we investigate the allowed as well as hindered transitions of orbitally excited Bc-meson states and predict their decay widths in overall agreement with other model predictions. We consider the typical case of Bc*(1 s )→Bc(1 s )γ , where our predicted decay width which is found quite sensitive to the mass difference between Bc* and Bc mesons may help in determining the mass of Bc* experimentally.

The competition of hydrogen-like and isotropic interactions on polymer collapse

NASA Astrophysics Data System (ADS)

Krawczyk, J.; Owczarek, A. L.; Prellberg, T.

2007-09-01

We investigate a lattice model of polymers where the nearest neighbour monomer monomer interaction strengths differ according to whether the local configurations have so-called 'hydrogen-like' formations or not. If the interaction strengths are all the same then the classical θ-point collapse transition occurs on lowering the temperature, and the polymer enters the isotropic liquid drop phase known as the collapsed globule. On the other hand, strongly favouring the hydrogen-like interactions gives rise to an anisotropic folded (solid-like) phase on lowering the temperature. We use Monte Carlo simulations up to a length of 256 to map out the phase diagram in the plane of parameters and determine the order of the associated phase transitions. We discuss the connections to semi-flexible polymers and other polymer models. Importantly, we demonstrate that for a range of energy parameters, two phase transitions occur on lowering the temperature, the second being a transition from the globule state to the crystal state. We argue from our data that this globule-to-crystal transition is continuous in two dimensions in accord with field-theory arguments concerning Hamiltonian walks, but is first order in three dimensions.

Structure of siderite FeCO[subscript 3] to 56 GPa and hysteresis of its spin-pairing transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lavina, Barbara; Dera, Przemyslaw; Downs, Robert T.

2010-09-17

The structure of siderite, FeCO{sub 3}, was determined to 56 GPa, beyond the spin-pairing transition of its iron d electrons. Fe{sup 2+} in the siderite structure is in the high-spin state at low pressures and transforms to the low-spin (LS) state over a narrow pressure range, 44 to 45 GPa, that is concomitant with a shrinkage of the octahedral bond distance by 4%, and a volume collapse of 10%. The structural rearrangements associated with the electronic transition are nearly isotropic in contrast with other properties of siderite, which mostly are highly anisotropic. Robust refinements of the crystal structure from single-crystalmore » x-ray diffraction data were performed at small pressure intervals in order to accurately evaluate the variation in the interatomic distances and to define the geometry of the carbonate hosting LS-Fe{sup 2+}. Thermal vibrations are remarkably lowered in the LS-Sd as shown by atomic displacement parameters. The formation of like-spin domains at the transition shows a hysteresis of more than 3 GPa, compatible with a strong cooperative contribution of neighboring clusters to the transition.« less

Stability and phase transition of skyrmion crystals generated by Dzyaloshinskii-Moriya interaction

NASA Astrophysics Data System (ADS)

El Hog, Sahbi; Bailly-Reyre, Aurélien; Diep, H. T.

2018-06-01

We generate a crystal of skyrmions in two dimensions using a Heisenberg Hamiltonian including the ferromagnetic interaction J, the Dzyaloshinskii-Moriya interaction D, and an applied magnetic field H. The ground state (GS) is determined by minimizing the interaction energy. We show that the GS is a skyrmion crystal in a region of (D, H) . The stability of this skyrmion crystalline phase at finite temperatures is shown by a study of the time-dependence of the order parameter using Monte Carlo simulations. We observe that the relaxation is very slow and follows a stretched exponential law. The skyrmion crystal phase is shown to undergo a transition to the paramagnetic state at a finite temperature.

Time delay induced different synchronization patterns in repulsively coupled chaotic oscillators

NASA Astrophysics Data System (ADS)

Yao, Chenggui; Yi, Ming; Shuai, Jianwei

2013-09-01

Time delayed coupling plays a crucial role in determining the system's dynamics. We here report that the time delay induces transition from the asynchronous state to the complete synchronization (CS) state in the repulsively coupled chaotic oscillators. In particular, by changing the coupling strength or time delay, various types of synchronous patterns, including CS, antiphase CS, antiphase synchronization (ANS), and phase synchronization, can be generated. In the transition regions between different synchronous patterns, bistable synchronous oscillators can be observed. Furthermore, we show that the time-delay-induced phase flip bifurcation is of key importance for the emergence of CS. All these findings may light on our understanding of neuronal synchronization and information processing in the brain.

Measurement of the {sup 157}Gd(n,{gamma}) reaction with the DANCE {gamma} calorimeter array

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chyzh, A.; Dashdorj, D.; Lawrence Livermore National Laboratory, Livermore, California 94551

2011-07-15

The {sup 157}Gd(n,{gamma}) reaction was measured with the DANCE {gamma} calorimeter (consisting of 160 BaF{sub 2} scintillation detectors) at the Los Alamos Neutron Science Center. The multiplicity distributions of the {gamma} decay were used to determine the resonance spins up to E{sub n}=300 eV. The {gamma}-ray energy spectra for different multiplicities were measured for the s-wave resonances. The shapes of these spectra were compared with simulations based on the use of the DICEBOX statistical model code. Simulations showed that the scissors mode is required not only for the ground-state transitions but also for transitions between excited states.

Determination of ground and excited state dipole moments of dipolar laser dyes by solvatochromic shift method.

PubMed

Patil, S K; Wari, M N; Panicker, C Yohannan; Inamdar, S R

2014-04-05

The absorption and fluorescence spectra of three medium sized dipolar laser dyes: coumarin 478 (C478), coumarin 519 (C519) and coumarin 523 (C523) have been recorded and studied comprehensively in various solvents at room temperature. The absorption and fluorescence spectra of C478, C519 and C523 show a bathochromic and hypsochromic shifts with increasing solvent polarity indicate that the transitions involved are π→π(∗) and n→π(∗). Onsager radii determined from ab initio calculations were used in the determination of dipole moments. The ground and excited state dipole moments were evaluated by using solvatochromic correlations. It is observed that the dipole moment values of excited states (μe) are higher than corresponding ground state values (μg) for the solvents studied. The ground and excited state dipole moments of these probes computed from ab initio calculations and those determined experimentally are compared and the results are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Stochastic approach to plasticity and yield in amorphous solids.

PubMed

Hentschel, H G E; Jaiswal, Prabhat K; Procaccia, Itamar; Sastry, Srikanth

2015-12-01

We focus on the probability distribution function (PDF) P(Δγ;γ) where Δγ are the measured strain intervals between plastic events in a athermal strained amorphous solids, and γ measures the accumulated strain. The tail of this distribution as Δγ→0 (in the thermodynamic limit) scales like Δγ(η). The exponent η is related via scaling relations to the tail of the PDF of the eigenvalues of the plastic modes of the Hessian matrix P(λ) which scales like λ(θ), η=(θ-1)/2. The numerical values of η or θ can be determined easily in the unstrained material and in the yielded state of plastic flow. Special care is called for in the determination of these exponents between these states as γ increases. Determining the γ dependence of the PDF P(Δγ;γ) can shed important light on plasticity and yield. We conclude that the PDF's of both Δγ and λ are not continuous functions of γ. In slowly quenched amorphous solids they undergo two discontinuous transitions, first at γ=0(+) and then at the yield point γ=γ(Y) to plastic flow. In quickly quenched amorphous solids the second transition is smeared out due to the nonexisting stress peak before yield. The nature of these transitions and scaling relations with the system size dependence of 〈Δγ〉 are discussed.

Narrow band noise response of a Belleville spring resonator.

PubMed

Lyon, Richard H

2013-09-01

This study of nonlinear dynamics includes (i) an identification of quasi-steady states of response using equivalent linearization, (ii) the temporal simulation of the system using Heun's time step procedure on time domain analytic signals, and (iii) a laboratory experiment. An attempt has been made to select material and measurement parameters so that nearly the same systems are used and analyzed for all three parts of the study. This study illustrates important features of nonlinear response to narrow band excitation: (a) states of response that the system can acquire with transitions of the system between those states, (b) the interaction between the noise source and the vibrating load in which the source transmits energy to or draws energy from the load as transitions occur; (c) the lag or lead of the system response relative to the source as transitions occur that causes the average frequencies of source and response to differ; and (d) the determination of the state of response (mass or stiffness controlled) by observation of the instantaneous phase of the influence function. These analyses take advantage of the use of time domain analytic signals that have a complementary role to functions that are analytic in the frequency domain.

Research investigation directed toward extending the useful range of the electromagnetic spectrum

NASA Technical Reports Server (NTRS)

Hartmann, S. R.

1971-01-01

The lifetimes and fine structure of He(-) were studied using time-of-flight techniques and quenching by a static axial magnetic field. Using level-crossing spectroscopy the hyperfine constants A and B and the lifetime of the 3 2P3/2 state of Li-7 were measured. Polarization of the Ru 7S level was created as a first step in determining the hyperfine structure of the alkali excited S state. The parametric interaction between light and microwaves in optically pumped Rb-87 vapor were investigated. Measurements and analyses of transitions in formaldehyde and its isotopic species and in the lowest two excited vibrational states of H2CO were also made, as well as of transitions in furan, pyrrole, formic acid, and cyanoacetylene. The Hanle effect was studied in the NO molecule, and RF oscillators were developed with flat, wideband output to observe excited state hyperfine transitions at zero field. Data was generated on the time-dependent behavior of photon echoes in ruby. Stimulated Raman scattering was studied in atomic Tl vapor. A Q switched, temperature-tuned ruby laser was developed which operates between 6934 and 6938 A. The frequency shift due to resonant interaction between identical radiating atoms was calculated.

How Accurate Are Transition States from Simulations of Enzymatic Reactions?

PubMed Central

2015-01-01

The rate expression of traditional transition state theory (TST) assumes no recrossing of the transition state (TS) and thermal quasi-equilibrium between the ground state and the TS. Currently, it is not well understood to what extent these assumptions influence the nature of the activated complex obtained in traditional TST-based simulations of processes in the condensed phase in general and in enzymes in particular. Here we scrutinize these assumptions by characterizing the TSs for hydride transfer catalyzed by the enzyme Escherichia coli dihydrofolate reductase obtained using various simulation approaches. Specifically, we compare the TSs obtained with common TST-based methods and a dynamics-based method. Using a recently developed accurate hybrid quantum mechanics/molecular mechanics potential, we find that the TST-based and dynamics-based methods give considerably different TS ensembles. This discrepancy, which could be due equilibrium solvation effects and the nature of the reaction coordinate employed and its motion, raises major questions about how to interpret the TSs determined by common simulation methods. We conclude that further investigation is needed to characterize the impact of various TST assumptions on the TS phase-space ensemble and on the reaction kinetics. PMID:24860275

Urea-temperature phase diagrams capture the thermodynamics of denatured state expansion that accompany protein unfolding.

PubMed

Tischer, Alexander; Auton, Matthew

2013-09-01

We have analyzed the thermodynamic properties of the von Willebrand factor (VWF) A3 domain using urea-induced unfolding at variable temperature and thermal unfolding at variable urea concentrations to generate a phase diagram that quantitatively describes the equilibrium between native and denatured states. From this analysis, we were able to determine consistent thermodynamic parameters with various spectroscopic and calorimetric methods that define the urea-temperature parameter plane from cold denaturation to heat denaturation. Urea and thermal denaturation are experimentally reversible and independent of the thermal scan rate indicating that all transitions are at equilibrium and the van't Hoff and calorimetric enthalpies obtained from analysis of individual thermal transitions are equivalent demonstrating two-state character. Global analysis of the urea-temperature phase diagram results in a significantly higher enthalpy of unfolding than obtained from analysis of individual thermal transitions and significant cross correlations describing the urea dependence of ΔH0 and ΔCP0 that define a complex temperature dependence of the m-value. Circular dichroism (CD) spectroscopy illustrates a large increase in secondary structure content of the urea-denatured state as temperature increases and a loss of secondary structure in the thermally denatured state upon addition of urea. These structural changes in the denatured ensemble make up ∼40% of the total ellipticity change indicating a highly compact thermally denatured state. The difference between the thermodynamic parameters obtained from phase diagram analysis and those obtained from analysis of individual thermal transitions illustrates that phase diagrams capture both contributions to unfolding and denatured state expansion and by comparison are able to decipher these contributions. © 2013 The Protein Society.

Atmospheric conditions during the spring and fall transitions in the coastal ocean off western United States

NASA Technical Reports Server (NTRS)

Strub, P. Ted; James, Corinne

1988-01-01

Atmospheric events which force the spring and fall oceanic transitions in the coastal ocean off the west coast of North America were examined by analyzing the records of adjusted sea level (ASL), coastal wind stress, sea level atmospheric pressure (SLP), and 500-mbar heights for the years 1971-1975 and 1980-1983. The records cover periods of 91 days, centered on the dates of the spring and fall transitions as determined from coastal ASL data. It was found that the dominant mode of the ASL and coastal wind stress are similar around the times of both the spring and fall transitions, and that the time series for these modes are highly correlated with one another. Principal estimator patterns show the spatial patterns of SLP which force the ASL and coastal wind stress during the transitions.

Pressure-induced Td to 1T' structural phase transition in WTe 2

DOE PAGES

Zhou, Yonghui; Chen, Xuliang; Li, Nana; ...

2016-07-01

WTe 2 is provoking immense interest owing to its extraordinary properties, such as large positive magnetoresistance, pressure-driven superconductivity and possible type-II Weyl semimetal state. Here we report results of high-pressure synchrotron X-ray diffraction (XRD), Raman and electrical transport measurements on WTe 2. Both the XRD and Raman results reveal a structural transition upon compression, starting at 6.0 GPa and completing above 15.5 GPa. We have determined that the high-pressure lattice symmetry is monoclinic 1T' with space group of P21/m. This transition is related to a lateral sliding of adjacent Te-W-Te layers and results in a collapse of the unit cellmore » volume by ~20.5%. The structural transition also casts a pressure range with the broadened superconducting transition, where the zero resistance disappears.« less

Critical Behaviors in Contagion Dynamics.

PubMed

Böttcher, L; Nagler, J; Herrmann, H J

2017-02-24

We study the critical behavior of a general contagion model where nodes are either active (e.g., with opinion A, or functioning) or inactive (e.g., with opinion B, or damaged). The transitions between these two states are determined by (i) spontaneous transitions independent of the neighborhood, (ii) transitions induced by neighboring nodes, and (iii) spontaneous reverse transitions. The resulting dynamics is extremely rich including limit cycles and random phase switching. We derive a unifying mean-field theory. Specifically, we analytically show that the critical behavior of systems whose dynamics is governed by processes (i)-(iii) can only exhibit three distinct regimes: (a) uncorrelated spontaneous transition dynamics, (b) contact process dynamics, and (c) cusp catastrophes. This ends a long-standing debate on the universality classes of complex contagion dynamics in mean field and substantially deepens its mathematical understanding.

Transit traverse in Missouri, 1900-1937. Part 6, Northeastern Missouri, 1900-37

USGS Publications Warehouse

Staack, John George

1940-01-01

This bulletin, which for convenience is to be published in eight parts, contains the results of all transit traverse* done In Missouri through 1937 by the Geological Survey, United States Department of the Interior, including those heretofore published. (See page X.) Each of the parts deals with one of eight sections into which the State has been divided for this purpose and which have been designated northeastern, northwestern, southeastern, southwestern, central, east-central, south-central, and west-central Missouri. In each part descriptions of the points for which geodetic positions have been determined are listed according to the quadrangles in which the points occur. Results of transit traverse other than that done by the Geological Survey have not been included.Northeastern Missouri, as the term is used in this bulletin and as the subject of part 6 of the bulletin, is, as its name indicates, the north-easternmost section of the State. Its north and east boundaries are the boundaries of the State; its west and south boundaries are formed by a line that runs south along longitude 93°15' to latitude 39°30', thence east to longitude 92°00', thence south to latitude 39°15', thence east to the east boundary of the State.

Spectroscopy of the 1/2 2S → 3/2 2P transition in Yb ii: Isotope shifts, hyperfine splitting, and branching ratios

NASA Astrophysics Data System (ADS)

Feldker, T.; Fürst, H.; Ewald, N. V.; Joger, J.; Gerritsma, R.

2018-03-01

We report on spectroscopic results on the 1/2 2S → 3/2 2P transition in single trapped Yb+ ions. We measure the isotope shifts for all stable Yb+ isotopes except +173Yb, as well as the hyperfine splitting of the 3/2 2P state in +171Yb. Our results are in agreement with previous measurements but are a factor of 5-9 more precise. For the hyperfine constant A (3/2 2P)=875.4 (10 )MHz our results also agree with previous measurements but deviate significantly from theoretical predictions. We present experimental results on the branching ratios for the decay of the 3/2 2P state. We find branching fractions for the decay to the 3/2 2D state and 5/2 2D state of 0.17(1)% and 1.08(5)%, respectively, in rough agreement with theoretical predictions. Furthermore, we measured the isotope shifts of the 7/2 2F →1D[5/2 ] 5 /2 transition and determine the hyperfine structure constant for the 1D[5/2 ] 5 /2 state in +171Yb to be A (1D[5/2 ] 5 /2)=-107 (6 ) MHz .

Pressure-induced electronic topological transitions in the charge-density-wave material In 4 Se 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yuhang; Song, Liyan; Shao, Xuecheng

2017-08-01

High-pressure in situ angle dispersive X-ray diffraction (ADXRD) measurements were performed on the charge-density-wave (CDW) material In4Se3 up to 48.8 GPa. Pressure-induced structural changes were observed at 7.0 and 34.2 GPa, respectively. Using the CALYPSO methodology, the first high-pressure phase was solved as an exotic Pca21 structure. The compressional behaviors of the initial Pnnm and the Pca21 phases were all determined. Combined with first-principle calculations, we find that, unexpectedly, the Pnnm phase probably experiences twice electronic topological transitions (ETTs), from the initial possible CDW state to a semimetallic state at about 2.3 GPa and then back to a possible CDWmore » state at around 3.5 GPa, which was uncovered for the first time in CDW systems. In the both possible CDW states, pressure provokes a decrease of band-gap. The observation of a bulk metallic state was ascribed to structural transition to the Pca21 phase. Besides, based on electronic band structure calculations, the thermoelectric property of the Pnnm phase under compression was discussed. Our results show that pressure play a dramatic role in tuning In4Se3's structure and transport properties.« less

Phase Transition in a Healthy Human Heart Rate

NASA Astrophysics Data System (ADS)

Kiyono, Ken; Struzik, Zbigniew R.; Aoyagi, Naoko; Togo, Fumiharu; Yamamoto, Yoshiharu

2005-07-01

A healthy human heart rate displays complex fluctuations which share characteristics of physical systems in a critical state. We demonstrate that the human heart rate in healthy individuals undergoes a dramatic breakdown of criticality characteristics, reminiscent of continuous second order phase transitions. By studying the germane determinants, we show that the hallmark of criticality—highly correlated fluctuations—is observed only during usual daily activity, and a breakdown of these characteristics occurs in prolonged, strenuous exercise and sleep. This finding is the first reported discovery of the dynamical phase transition phenomenon in a biological control system and will be a key to understanding the heart rate control system in health and disease.

Binding energies and spatial structures of small carrier complexes in monolayer transition-metal dichalcogenides via diffusion Monte Carlo

DOE PAGES

Mayers, Matthew Z.; Berkelbach, Timothy C.; Hybertsen, Mark S.; ...

2015-10-09

Ground-state diffusion Monte Carlo is used to investigate the binding energies and intercarrier radial probability distributions of excitons, trions, and biexcitons in a variety of two-dimensional transition-metal dichalcogenide materials. We compare these results to approximate variational calculations, as well as to analogous Monte Carlo calculations performed with simplified carrier interaction potentials. Our results highlight the successes and failures of approximate approaches as well as the physical features that determine the stability of small carrier complexes in monolayer transition-metal dichalcogenide materials. In conclusion, we discuss points of agreement and disagreement with recent experiments.

Parameter optimization on the convergence surface of path simulations

NASA Astrophysics Data System (ADS)

Chandrasekaran, Srinivas Niranj

Computational treatments of protein conformational changes tend to focus on the trajectories themselves, despite the fact that it is the transition state structures that contain information about the barriers that impose multi-state behavior. PATH is an algorithm that computes a transition pathway between two protein crystal structures, along with the transition state structure, by minimizing the Onsager-Machlup action functional. It is rapid but depends on several unknown input parameters whose range of different values can potentially generate different transition-state structures. Transition-state structures arising from different input parameters cannot be uniquely compared with those generated by other methods. I outline modifications that I have made to the PATH algorithm that estimates these input parameters in a manner that circumvents these difficulties, and describe two complementary tests that validate the transition-state structures found by the PATH algorithm. First, I show that although the PATH algorithm and two other approaches to computing transition pathways produce different low-energy structures connecting the initial and final ground-states with the transition state, all three methods agree closely on the configurations of their transition states. Second, I show that the PATH transition states are close to the saddle points of free-energy surfaces connecting initial and final states generated by replica-exchange Discrete Molecular Dynamics simulations. I show that aromatic side-chain rearrangements create similar potential energy barriers in the transition-state structures identified by PATH for a signaling protein, a contractile protein, and an enzyme. Finally, I observed, but cannot account for, the fact that trajectories obtained for all-atom and Calpha-only simulations identify transition state structures in which the Calpha atoms are in essentially the same positions. The consistency between transition-state structures derived by different algorithms for unrelated protein systems argues that although functionally important protein conformational change trajectories are to a degree stochastic, they nonetheless pass through a well-defined transition state whose detailed structural properties can rapidly be identified using PATH. In the end, I outline the strategies that could enhance the efficiency and applicability of PATH.

Evolution of E 2 transition strength in deformed hafnium isotopes from new measurements on 172Hf,174Hf, and 176Hf

NASA Astrophysics Data System (ADS)

Rudigier, M.; Nomura, K.; Dannhoff, M.; Gerst, R.-B.; Jolie, J.; Saed-Samii, N.; Stegemann, S.; Régis, J.-M.; Robledo, L. M.; Rodríguez-Guzmán, R.; Blazhev, A.; Fransen, Ch.; Warr, N.; Zell, K. O.

2015-04-01

Background: The available data for E 2 transition strengths in the region between neutron-deficient hafnium and platinum isotopes are far from complete. More and precise data are needed to enhance the picture of structure evolution in this region and to test state-of-the-art nuclear models. In a simple model, the maximum collectivity is expected at the middle of the major shell. However, for actual nuclei, particularly in heavy-mass regions, which should be highly complex, this picture may no longer be the case, and one should use a more realistic nuclear-structure model. We address this point by studying the spectroscopy of Hf as a representative case. Purpose: We remeasure the 21+ half-lives of 172,174,176Hf, for which there is some disagreement in the literature. The main goal is to measure, for the first time, the half-lives of higher-lying states of the rotational band. The new results are compared to a theoretical calculation for absolute transition strengths. Method: The half-lives were measured using γ -γ and conversion-electron-γ delayed coincidences with the fast timing method. For the determination of half-lives in the picosecond region, the generalized centroid difference method was applied. For the theoretical calculation of the spectroscopic properties, the interacting boson model is employed, whose Hamiltonian is determined based on microscopic energy-density functional calculations. Results: The measured 21+ half-lives disagree with results from earlier γ -γ fast timing measurements, but are in agreement with data from Coulomb excitation experiments and other methods. Half-lives of the 41+ and 61+ states were measured, as well as a lower limit for the 81+ states. Conclusions: This work shows the importance of a mass-dependent effective boson charge in the interacting boson model for the description of E 2 transition rates in chains of nuclei. It encourages further studies of the microscopic origin of this mass dependence. New experimental values on transition rates in nuclei from neighboring isotopic chains could support these studies.

Mapping the Dynamics Landscape of Conformational Transitions in Enzyme: The Adenylate Kinase Case

PubMed Central

Li, Dechang; Liu, Ming S.; Ji, Baohua

2015-01-01

Conformational transition describes the essential dynamics and mechanism of enzymes in pursuing their various functions. The fundamental and practical challenge to researchers is to quantitatively describe the roles of large-scale dynamic transitions for regulating the catalytic processes. In this study, we tackled this challenge by exploring the pathways and free energy landscape of conformational changes in adenylate kinase (AdK), a key ubiquitous enzyme for cellular energy homeostasis. Using explicit long-timescale (up to microseconds) molecular dynamics and bias-exchange metadynamics simulations, we determined at the atomistic level the intermediate conformational states and mapped the transition pathways of AdK in the presence and absence of ligands. There is clearly chronological operation of the functional domains of AdK. Specifically in the ligand-free AdK, there is no significant energy barrier in the free energy landscape separating the open and closed states. Instead there are multiple intermediate conformational states, which facilitate the rapid transitions of AdK. In the ligand-bound AdK, the closed conformation is energetically most favored with a large energy barrier to open it up, and the conformational population prefers to shift to the closed form coupled with transitions. The results suggest a perspective for a hybrid of conformational selection and induced fit operations of ligand binding to AdK. These observations, depicted in the most comprehensive and quantitative way to date, to our knowledge, emphasize the underlying intrinsic dynamics of AdK and reveal the sophisticated conformational transitions of AdK in fulfilling its enzymatic functions. The developed methodology can also apply to other proteins and biomolecular systems. PMID:26244746

Structural basis for the mechanism and substrate specificity of glycocyamine kinase, a phosphagen kinase family member

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, Kap; Pullalarevu, Sadhana; Surabian, Karen Talin

2010-03-12

Glycocyamine kinase (GK), a member of the phosphagen kinase family, catalyzes the Mg{sup 2+}-dependent reversible phosphoryl group transfer of the N-phosphoryl group of phosphoglycocyamine to ADP to yield glycocyamine and ATP. This reaction helps to maintain the energy homeostasis of the cell in some multicelullar organisms that encounter high and variable energy turnover. GK from the marine worm Namalycastis sp. is heterodimeric, with two homologous polypeptide chains, {alpha} and {beta}, derived from a common pre-mRNA by mutually exclusive N-terminal alternative exons. The N-terminal exon of GK{beta} encodes a peptide that is different in sequence and is 16 amino acids longermore » than that encoded by the N-terminal exon of GK{alpha}. The crystal structures of recombinant GK{alpha}{beta} and GK{beta}{beta} from Namalycastis sp. were determined at 2.6 and 2.4 {angstrom} resolution, respectively. In addition, the structure of the GK{beta}{beta} was determined at 2.3 {angstrom} resolution in complex with a transition state analogue, Mg{sup 2+}-ADP-NO{sub 3}{sup -}-glycocyamine. Consistent with the sequence homology, the GK subunits adopt the same overall fold as that of other phosphagen kinases of known structure (the homodimeric creatine kinase (CK) and the monomeric arginine kinase (AK)). As with CK, the GK N-termini mediate the dimer interface. In both heterodimeric and homodimeric GK forms, the conformations of the two N-termini are asymmetric, and the asymmetry is different than that reported previously for the homodimeric CKs from several organisms. The entire polypeptide chains of GK{alpha}{beta} are structurally defined, and the longer N-terminus of the {beta} subunit is anchored at the dimer interface. In GK{beta}{beta} the 24 N-terminal residues of one subunit and 11 N-terminal residues of the second subunit are disordered. This observation is consistent with a proposal that the GK{alpha}{beta} amino acids involved in the interface formation were optimized once a heterodimer emerged as the physiological form of the enzyme. As a consequence, the homodimer interface (either solely {alpha} or solely {beta} chains) has been corrupted. In the unbound state, GK exhibits an open conformation analogous to that observed with ligand-free CK or AK. Upon binding the transition state analogue, both subunits of GK undergo the same closure motion that clasps the transition state analogue, in contrast to the transition state analogue complexes of CK, where the corresponding transition state analogue occupies only one subunit, which undergoes domain closure. The active site environments of the GK, CK, and AK at the bound states reveal the structural determinants of substrate specificity. Despite the equivalent binding in both active sites of the GK dimer, the conformational asymmetry of the N-termini is retained. Thus, the coupling between the structural asymmetry and negative cooperativity previously proposed for CK is not supported in the case of GK.« less

A stochastic hybrid systems based framework for modeling dependent failure processes

PubMed Central

Fan, Mengfei; Zeng, Zhiguo; Zio, Enrico; Kang, Rui; Chen, Ying

2017-01-01

In this paper, we develop a framework to model and analyze systems that are subject to dependent, competing degradation processes and random shocks. The degradation processes are described by stochastic differential equations, whereas transitions between the system discrete states are triggered by random shocks. The modeling is, then, based on Stochastic Hybrid Systems (SHS), whose state space is comprised of a continuous state determined by stochastic differential equations and a discrete state driven by stochastic transitions and reset maps. A set of differential equations are derived to characterize the conditional moments of the state variables. System reliability and its lower bounds are estimated from these conditional moments, using the First Order Second Moment (FOSM) method and Markov inequality, respectively. The developed framework is applied to model three dependent failure processes from literature and a comparison is made to Monte Carlo simulations. The results demonstrate that the developed framework is able to yield an accurate estimation of reliability with less computational costs compared to traditional Monte Carlo-based methods. PMID:28231313

A stochastic hybrid systems based framework for modeling dependent failure processes.

PubMed

Fan, Mengfei; Zeng, Zhiguo; Zio, Enrico; Kang, Rui; Chen, Ying

2017-01-01

In this paper, we develop a framework to model and analyze systems that are subject to dependent, competing degradation processes and random shocks. The degradation processes are described by stochastic differential equations, whereas transitions between the system discrete states are triggered by random shocks. The modeling is, then, based on Stochastic Hybrid Systems (SHS), whose state space is comprised of a continuous state determined by stochastic differential equations and a discrete state driven by stochastic transitions and reset maps. A set of differential equations are derived to characterize the conditional moments of the state variables. System reliability and its lower bounds are estimated from these conditional moments, using the First Order Second Moment (FOSM) method and Markov inequality, respectively. The developed framework is applied to model three dependent failure processes from literature and a comparison is made to Monte Carlo simulations. The results demonstrate that the developed framework is able to yield an accurate estimation of reliability with less computational costs compared to traditional Monte Carlo-based methods.

Solvable four-state Landau-Zener model of two interacting qubits with path interference

DOE PAGES

Sinitsyn, Nikolai A.

2015-11-30

In this paper, I identify a nontrivial four-state Landau-Zener model for which transition probabilities between any pair of diabatic states can be determined analytically and exactly. The model describes an experimentally accessible system of two interacting qubits, such as a localized state in a Dirac material with both valley and spin degrees of freedom or a singly charged quantum dot (QD) molecule with spin orbit coupling. Application of the linearly time-dependent magnetic field induces a sequence of quantum level crossings with possibility of interference of different trajectories in a semiclassical picture. I argue that this system satisfies the criteria ofmore » integrability in the multistate Landau-Zener theory, which allows one to derive explicit exact analytical expressions for the transition probability matrix. Finally, I also argue that this model is likely a special case of a larger class of solvable systems, and present a six-state generalization as an example.« less

An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goings, Joshua J.; Li, Xiaosong, E-mail: xsli@uw.edu

2016-06-21

One of the challenges of interpreting electronic circular dichroism (ECD) band spectra is that different states may have different rotatory strength signs, determined by their absolute configuration. If the states are closely spaced and opposite in sign, observed transitions may be washed out by nearby states, unlike absorption spectra where transitions are always positive additive. To accurately compute ECD bands, it is necessary to compute a large number of excited states, which may be prohibitively costly if one uses the linear-response time-dependent density functional theory (TDDFT) framework. Here we implement a real-time, atomic-orbital based TDDFT method for computing the entiremore » ECD spectrum simultaneously. The method is advantageous for large systems with a high density of states. In contrast to previous implementations based on real-space grids, the method is variational, independent of nuclear orientation, and does not rely on pseudopotential approximations, making it suitable for computation of chiroptical properties well into the X-ray regime.« less

Interictal to Ictal Phase Transition in a Small-World Network

NASA Astrophysics Data System (ADS)

Nemzer, Louis; Cravens, Gary; Worth, Robert

Real-time detection and prediction of seizures in patients with epilepsy is essential for rapid intervention. Here, we perform a full Hodgkin-Huxley calculation using n 50 in silico neurons configured in a small-world network topology to generate simulated EEG signals. The connectivity matrix, constructed using a Watts-Strogatz algorithm, admits randomized or deterministic entries. We find that situations corresponding to interictal (non-seizure) and ictal (seizure) states are separated by a phase transition that can be influenced by congenital channelopathies, anticonvulsant drugs, and connectome plasticity. The interictal phase exhibits scale-free phenomena, as characterized by a power law form of the spectral power density, while the ictal state suffers from pathological synchronization. We compare the results with intracranial EEG data and show how these findings may be used to detect or even predict seizure onset. Along with the balance of excitatory and inhibitory factors, the network topology plays a large role in determining the overall characteristics of brain activity. We have developed a new platform for testing the conditions that contribute to the phase transition between non-seizure and seizure states.

In-Situ Phase Transition Control in the Supercooled State for Robust Active Glass Fiber.

PubMed

Lv, Shichao; Cao, Maoqing; Li, Chaoyu; Li, Jiang; Qiu, Jianrong; Zhou, Shifeng

2017-06-21

The construction of a dopant-activated photonic composite is of great technological importance for various applications, including smart lighting, optical amplification, laser, and optical detection. The bonding arrangement around the introduced dopants largely determines the properties, yet it remains a daunting challenge to manipulate the local state of the matrix (i.e., phase) inside the transparent composite in a controllable manner. Here we demonstrate that the relaxation of the supercooled state enables in-situ phase transition control in glass. Benefiting from the unique local atom arrangement manner, the strategy offers the possibility for simultaneously tuning the chemical environment of the incorporated dopant and engineering the dopant-host interaction. This allows us to effectively activate the dopant with high efficiency (calculated as ∼100%) and profoundly enhance the dopant-host energy-exchange interaction. Our results highlight that the in-situ phase transition control in glass may provide new opportunities for fabrication of unusual photonic materials with intense broadband emission at ∼1100 nm and development of the robust optical detection unit with high compactness and broadband photon-harvesting capability (from X-ray to ultraviolet light).

The Mystery of the Electronic Spectrum of Ruthenium Monophosphide

NASA Astrophysics Data System (ADS)

Adam, Allan G.; Christensen, Ryan M.; Dore, Jacob M.; Konder, Ricarda M.; Tokaryk, Dennis W.

2016-06-01

Using PH3 as a reactant gas and ruthenium as the target metal in the UNB laser ablation spectrometer, the ruthenium monophosphide molecule (RuP) has been detected. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra of two vibrational bands at 577nm and 592nm have been taken; the bands have been identified as 1-0 and 0-0 bands based on isotopic shifts. Ruthenium has seven stable isotopes and rotational transitions have been observed for six of the RuP isotopologues. RuP is isoelectronic to RuN so it is expected that RuP will have a 2Σ+ ground state and low resolution spectra indicated a likely 2Σ+ - 2Σ+ electronic transition. Further investigation has led us to believe we are observing a 2Π - 2Σ+ transition but mysteriously some important rotational branches are missing. It is hoped that new data to be recorded on a second electronic system we have observed at 535nm will help shed light on this mystery.

Elastic Model Transitions: A Hybrid Approach Utilizing Quadratic Inequality Constrained Least Squares (LSQI) and Direct Shape Mapping (DSM)

NASA Technical Reports Server (NTRS)

Hannan, Mike R.; Jurenko, Robert J.; Bush, Jason; Ottander, John

2014-01-01

A method for transitioning linear time invariant (LTI) models in time varying simulation is proposed that utilizes a hybrid approach for determining physical displacements by augmenting the original quadratically constrained least squares (LSQI) algorithm with Direct Shape Mapping (DSM) and modifying the energy constraints. The approach presented is applicable to simulation of the elastic behavior of launch vehicles and other structures that utilize discrete LTI finite element model (FEM) derived mode sets (eigenvalues and eigenvectors) that are propagated throughout time. The time invariant nature of the elastic data presents a problem of how to properly transition elastic states from the prior to the new model while preserving motion across the transition and ensuring there is no truncation or excitation of the system. A previous approach utilizes a LSQI algorithm with an energy constraint to effect smooth transitions between eigenvector sets with no requirement that the models be of similar dimension or have any correlation. This approach assumes energy is conserved across the transition, which results in significant non-physical transients due to changing quasi-steady state energy between mode sets, a phenomenon seen when utilizing a truncated mode set. The computational burden of simulating a full mode set is significant so a subset of modes is often selected to reduce run time. As a result of this truncation, energy between mode sets may not be constant and solutions across transitions could produce non-physical transients. In an effort to abate these transients an improved methodology was developed based on the aforementioned approach, but this new approach can handle significant changes in energy across mode set transitions. It is proposed that physical velocities due to elastic behavior be solved for using the LSQI algorithm, but solve for displacements using a two-step process that independently addresses the quasi-steady-state and non-steady-state contributions to the elastic displacement. For structures subject to large external forces, such as thrust or atmospheric drag, it is imperative to capture these forces when solving for elastic displacement. To simplify the mathematical formulation, assumptions are made regarding mass matrix normalization, constant external forcing, and constant viscous damping. These simplifications allow for direct solutions to the quasi-steady-state displacements through a process titled Direct Shape Mapping. DSM solves for the displacements using the eigenvalues of the elastic modes and the external forcing and returns a set of elastic displacements dictated by the eigenvectors of the post-transition mode set. For the non-steady-state contributions to displacement we formulate a LSQI problem that is constrained by energy of the non-steady state terms. The contributions from the quasi-steady-state and non-steady state solutions are then combined to obtain the physical displacements associated with the new set of eigenvectors. Results for the LSQI-DSM approach show significant reduction/complete removal of transients across mode set transitions while maintaining elastic motion from the prior state. For time propagation applications employing discrete elastic models that need to be transitioned in time and where running with full a full mode set is not feasible, the method developed offers a practical solution to simulating vehicle elasticity.

The importance of atomic and molecular correlation on the bonding in transition metal compounds

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Walch, Stephen P.

1986-01-01

The determination of accurate spectroscopic parameters for molecular systems containing transition metal atoms is shown to require extensive data sets and a high level correlation treatment, and techniques and their limitations are considered. Extensive results reported on the transition metal atoms, hydrides, oxides, and dimers makes possible the design of a calculation to correctly describe the mixing of different atomic asymptotes, and to give a correct balance between molecular bonding and exchange interactions. Examples considered include the dipole moment of the 2Delta state of NiH, which can help determine the mixture of 3d(8)4s(2) and 3d(9)4s(1) in the NiH wavefunction, and the bonding in CrO, where an equivalent description of the relative energies associated with the Cr 3d-3d atomic exchange and the Cr-O bond is important.

Meson electro-/photo-production from QCD

DOE PAGES

Briceno, Raul A.

2016-07-02

I present the calculation of themore » $$\\pi^+\\gamma^\\star\\to\\pi^+\\pi^0$$ transition amplitude from quantum chromodynamics performed by the Hadron Spectrum Collaboration. The amplitude is determined for a range of values of the photon virtuality and the final state energy. One observes a clear dynamical enhancement due to the presence of the $$\\rho$$ resonance. By fitting the transition amplitude and analytically continuing it onto the $$\\rho$$-pole, the $$\\rho\\to\\pi\\gamma^\\star$$ form factor is obtained. This exploratory calculation, performed using lattice quantum chromodynamics, constitutes the very first determination of an electroweak decay of a hadronic resonance directly from the fundamental theory of quarks and gluons. In this talk, I highlight some of the necessary steps that made this calculation possible, placing emphasis on recently developed formalism. In conclusion, I discuss the status and outlook of the field for the study of $$N\\gamma^\\star\\to N^\\star\\to N\\pi$$ transitions.« less

Calorimetry of a Bose–Einstein-condensed photon gas

PubMed Central

Damm, Tobias; Schmitt, Julian; Liang, Qi; Dung, David; Vewinger, Frank; Weitz, Martin; Klaers, Jan

2016-01-01

Phase transitions, as the condensation of a gas to a liquid, are often revealed by a discontinuous behaviour of thermodynamic quantities. For liquid helium, for example, a divergence of the specific heat signals the transition from the normal fluid to the superfluid state. Apart from liquid helium, determining the specific heat of a Bose gas has proven to be a challenging task, for example, for ultracold atomic Bose gases. Here we examine the thermodynamic behaviour of a trapped two-dimensional photon gas, a system that allows us to spectroscopically determine the specific heat and the entropy of a nearly ideal Bose gas from the classical high temperature to the Bose-condensed quantum regime. The critical behaviour at the phase transition is clearly revealed by a cusp singularity of the specific heat. Regarded as a test of quantum statistical mechanics, our results demonstrate a quantitative agreement with its predictions at the microscopic level. PMID:27090978

CH3D photomixing spectroscopy up to 2.5 THz: New set of rotational and dipole parameters, first THz self-broadening measurements

NASA Astrophysics Data System (ADS)

Bray, Cédric; Cuisset, Arnaud; Hindle, Francis; Bocquet, Robin; Mouret, Gaël; Drouin, Brian J.

2017-03-01

Several previously unmeasured transitions of 12CH3D have been recorded by a terahertz photomixing continuous-wave spectrometer up to QR(10) branch at 2.5 THz. An improved set of rotational constants has been obtained utilizing a THz frequency metrology based on a frequency comb that achieved an averaged frequency position better than 150 kHz on more than fifty ground-state transitions. A detailed analysis of the measured line intensities was undertaken using the multispectrum fitting program and has resulted in a determination of new dipole moment parameters. Measurements at different pressures of the QR(7) transitions provide the first determination of self-broadening coefficients from pure rotational CH3D lines. The THz rotational measurements are consistent with IR rovibrational data but no significant vibrational dependence of self-broadening coefficient may be observed by comparison.

Temperature dependent photoreflectance and photoluminescence characterization of GaInNAs /GaAs single quantum well structures

NASA Astrophysics Data System (ADS)

Chen, T. H.; Huang, Y. S.; Lin, D. Y.; Tiong, K. K.

2004-12-01

Ga0.69In0.31NxAs1-x/GaAs single quantum well (SQW) structures with three different nitrogen compositions ( x =0%, 0.6%, and 0.9%) have been characterized, as functions of temperature in the range 10-300K, by the techniques of photoreflectance (PR) and photoluminescence (PL). In PR spectra, clear Franz-Keldysh oscillations (FKOs) above the GaAs band edge and the various excitonic transitions originating from the QW region have been observed. The built-in electric field in the SQW has been determined from FKOs and found to increase with N concentration. The PR signal has been found to decrease for nitrogen incorporated samples when the temperature was lowered due to a weakening of the modulation efficiency induced by carrier localization. A careful analysis of PR and PL spectra has led to the identification of various excitonic transitions, mnH(L), between the mth conduction band state and the nth heavy (light)-hole band state. The anomalous temperature dependent 11H transition energy and linewidth observed in the PL spectra have been explained as originating from the localized states as a result of nitrogen incorporation. The temperature dependence analysis yields information on the parameters that describe the temperature variations of the interband transitions.

Probing many-body localization with neural networks

NASA Astrophysics Data System (ADS)

Schindler, Frank; Regnault, Nicolas; Neupert, Titus

2017-06-01

We show that a simple artificial neural network trained on entanglement spectra of individual states of a many-body quantum system can be used to determine the transition between a many-body localized and a thermalizing regime. Specifically, we study the Heisenberg spin-1/2 chain in a random external field. We employ a multilayer perceptron with a single hidden layer, which is trained on labeled entanglement spectra pertaining to the fully localized and fully thermal regimes. We then apply this network to classify spectra belonging to states in the transition region. For training, we use a cost function that contains, in addition to the usual error and regularization parts, a term that favors a confident classification of the transition region states. The resulting phase diagram is in good agreement with the one obtained by more conventional methods and can be computed for small systems. In particular, the neural network outperforms conventional methods in classifying individual eigenstates pertaining to a single disorder realization. It allows us to map out the structure of these eigenstates across the transition with spatial resolution. Furthermore, we analyze the network operation using the dreaming technique to show that the neural network correctly learns by itself the power-law structure of the entanglement spectra in the many-body localized regime.

Estimation of State Transition Probabilities: A Neural Network Model

NASA Astrophysics Data System (ADS)

Saito, Hiroshi; Takiyama, Ken; Okada, Masato

2015-12-01

Humans and animals can predict future states on the basis of acquired knowledge. This prediction of the state transition is important for choosing the best action, and the prediction is only possible if the state transition probability has already been learned. However, how our brains learn the state transition probability is unknown. Here, we propose a simple algorithm for estimating the state transition probability by utilizing the state prediction error. We analytically and numerically confirmed that our algorithm is able to learn the probability completely with an appropriate learning rate. Furthermore, our learning rule reproduced experimentally reported psychometric functions and neural activities in the lateral intraparietal area in a decision-making task. Thus, our algorithm might describe the manner in which our brains learn state transition probabilities and predict future states.

Colloidal Disorder-Order Transition Experiment Probes Particle Interactions in Microgravity

NASA Technical Reports Server (NTRS)

1997-01-01

Everything in the universe is made up of the same basic building blocks - atoms. All physical properties of matter such as weight, hardness, and color are determined by the kind of atoms present and the way they interact with each other. The Colloidal Disorder-Order Transition (CDOT) shuttle flight experiment tested fundamental theories that model atomic interactions. The experiment was part of the Second United States Microgravity Laboratory (USML-2) aboard the Space Shuttle Columbia, which flew from October 20 to November 5, 1995.

Observation of a quadrupole interaction for cubic imperfections exhibiting a dynamic Jahn-Teller effect.

NASA Technical Reports Server (NTRS)

Herrington, J. R.; Estle, T. L.; Boatner, L. A.

1972-01-01

The observation and interpretation of weak EPR transitions, identified as 'forbidden' transitions, establish the existence of a new type of quadrupole interaction for cubic-symmetry imperfections. This interaction is simply a consequence of the ground-vibronic-state degeneracy. The signs as well as the magnitudes of the quadrupole-coupling coefficients are determined experimentally. These data agree well with the predictions of crystal field theory modified to account for a weak-to-moderate vibronic interaction (i.e., a dynamic Jahn-Teller effect).

Transition métal—isolant dans V 1-xMn xO 2-2xF 2x (0 < x ≤ 0, 10)étude des propriétés structurales, magnétiques, etélectriques

NASA Astrophysics Data System (ADS)

Akroune, A.; Casalot, A.

1987-05-01

V 1- xMn xO 2-2 xF 2 x samples (0 < x ≤ 0, 10) have been prepared by solid state reaction in sealed platinium tubes. The metal ⇄ insulator transition occurs at a quickly decreasing temperatures as MnF 2 increases. The crystallographic, magnetic, transport properties, and DTA have been determined and discussed.

Markov chains: computing limit existence and approximations with DNA.

PubMed

Cardona, M; Colomer, M A; Conde, J; Miret, J M; Miró, J; Zaragoza, A

2005-09-01

We present two algorithms to perform computations over Markov chains. The first one determines whether the sequence of powers of the transition matrix of a Markov chain converges or not to a limit matrix. If it does converge, the second algorithm enables us to estimate this limit. The combination of these algorithms allows the computation of a limit using DNA computing. In this sense, we have encoded the states and the transition probabilities using strands of DNA for generating paths of the Markov chain.

Micro-XANES Determination Fe Speciation in Natural Basalts at Mantle-Relevant fO2

NASA Astrophysics Data System (ADS)

Fischer, R.; Cottrell, E.; Lanzirotti, A.; Kelley, K. A.

2007-12-01

We demonstrate that the oxidation state of iron (Fe3+/ΣFe) can be determined with a precision of ±0.02 (10% relative) on natural basalt glasses at mantle-relevant fO2 using Fe K-edge X-ray absorption near edge structure (XANES) spectroscopy. This is equivalent to ±0.25 log unit resolution relative to the QFM buffer. Precise determination of the oxidation state over this narrow range (Fe3+/ΣFe=0.06-0.30) and at low fO2 (down to QFM-2) relies on appropriate standards, high spectral resolution, and highly reproducible methods for extracting the pre-edge centroid position. We equilibrated natural tholeiite powder in a CO/CO2 gas mixing furnace at 1350°C from QFM-3 to QFM+2 to create six glasses of known Fe3+/ΣFe, independently determined by Mössbauer spectroscopy. XANES spectra were collected at station X26A at NSLS, Brookhaven Natl. Lab, in fluorescence mode (9 element Ge array detector) using both Si(111) and Si(311) monochromators. Generally, the energy position of the 1s→3d (pre-edge) transition centroid is the most sensitive monitor of Fe oxidation state using XANES. For the mixture of Fe oxidation states in these glasses and the resulting coordination geometries, the pre-edge spectra are best defined by two multiple 3d crystal field transitions. The Si(311) monochromator, with higher energy resolution, substantially improved spectral resolution for the 1s→3d transition. Dwell times of 5s at 0.1eV intervals across the pre-edge region yielded spectra with the 1s→3d transition peaks clearly resolved. The pre-edge centroid position is highly sensitive to the background subtraction and peak fitting procedures. Differences in fitting models result in small but significant differences in the calculated peak area of each pre-edge multiplet, and the relative contribution of each peak to the calculated centroid. We assessed several schemes and obtained robust centroid positions by simultaneously fitting the background with a damped harmonic oscillator (DHO) function and pre-edge features with two Gaussians over a sub-sample of the pre-edge region (7110-7120 eV). We found that the relation between Fe3+/ΣFe and the centroid energy is non-linear over this fO2 range, which is expected if the coordination environment changes with oxidation state. ΔQFM is linearly related (R2=0.99) to the centroid position. This new calibration allows the oxidation states of natural mantle melts to be discriminated with high spatial resolution (9μm). We apply the new calibration to determination of Fe3+/ΣFe in natural basaltic glasses and olivine-hosted glass inclusions (Cottrell et al. & Kelley et al., this meeting).

Spectroscopy of selected metal-containing diatomic molecules

NASA Astrophysics Data System (ADS)

Gordon, Iouli E.

Fourier transform infrared emission spectra of MnH and MnD were observed in the ground X7Sigma+ electronic state. The vibration-rotation bands from v = 1 → 0 to v = 3 → 2 for MnH, and from v = 1 → 0 to v = 4 → 3 for MnD were recorded at an instrumental resolution of 0.0085 cm-1. Spectroscopic constants were determined for each vibrational level and equilibrium constants were found from a Dunham-type fit. The equilibrium vibrational constant oe for MnH was found to be 1546.84518(65) cm-1, the equilibrium rotational constant Be was found to be 5.6856789(103) cm-1 and the equilibrium bond distance re was determined to be 1.7308601(47) A. New high resolution emission spectra of CoH and CoD molecules have been recorded in the 640 nm to 3.5 mum region using a Fourier transform spectrometer. Many bands were observed for the A'3phi- X3phi electronic transition of CoH and CoD. In addition, a new [13.3]4 electronic state was found by observing the [13.3]4-X3phi3 and [13.3]4- X3phi4 transitions in the spectrum of CoD. Analysis of the transitions with DeltaO = 0, +/-1 provided more accurate values of spin-orbit splittings between O = 4 and O = 3 components. The ground state for both molecules was fitted both to band and Dunham-type constants. The estimated band constants of the perturbed upper states were also obtained. The emission spectrum of gas-phase YbO has been investigated using a Fourier transform spectrometer. A total of 8 red-degraded bands in the range 9 800--11 300 cm-1 were recorded at a resolution of 0.04 cm-1. Because of the multiple isotopomers present in the spectra, only 3 bands were rotationally analyzed. Perturbations were identified in two of these bands and all 3 transitions were found to terminate at the X1Sigma+ ground electronic state. The electronic configurations that give rise to the observed states are discussed and molecular parameters for all of the analyzed bands are reported. Electronic spectra of the previously unobserved EuH and EuD molecules were studied by means of Fourier transform spectroscopy and laser-induced fluorescence. The extreme complexity of these transitions made rotational assignments of EuH bands impossible. However, the spin-spin interaction constant, lambda, and Fermi contact parameter, bF, in the ground X9Sigma- electronic state were estimated for the 151EuH and 153EuH isotopologues. Electronic spectra of SmH, SmCl, TmH and ErF molecules were recorded for the first time using Fourier transform spectrometer. The poor signal to noise ratio of the observed bands coupled with their complexity prevented a rotational analysis. The electronic states that may be involved in the observed transitions are discussed.

Spectroscopy of selected metal-containing diatomic molecules

NASA Astrophysics Data System (ADS)

Gordon, Iouli

Fourier transform infrared emission spectra of MnH and MnD were observed in the ground X7[sigma]+ electronic state. The vibration-rotation bands from v = 1 to 0 to v = 3 to 2 for MnH, and from v = 1 to 0 to v = 4 to 3 for MnD were recorded at an instrumental resolution of 0. 0085 cm-1. Spectroscopic constants were determined for each vibrational level and equilibrium constants were found from a Dunham-type fit. The equilibrium vibrational constant [omega]e for MnH was found to be 1546. 84518(65) cm-1, the equilibrium rotational constant Be was found to be 5. 6856789(103) cm-1 and the equilibrium bond distance re was determined to be 1. 7308601(47) ?. New high resolution emission spectra of CoH and CoD molecules have been recorded in the 640 nm to 3. 5 _m region using a Fourier transform spectrometer. Many bands were observed for the A'3?-X3? electronic transition of CoH and CoD. In addition, a new [13. 3]4 electronic state was found by observing the [13. 3]4- X3?3 and [13. 3]4-X3?4 transitions in the spectrum of CoD. Analysis of the transitions with [delta][omega] = 0, ?1 provided more accurate values of spin-orbit splittings between [omega] = 4 and [omega] = 3 components. The ground state for both molecules was fitted both to band and Dunham-type constants. The estimated band constants of the perturbed upper states were also obtained. The emission spectrum of gas-phase YbO has been investigated using a Fourier transform spectrometer. A total of 8 red-degraded bands in the range 9 800 ? 11 300 cm-1 were recorded at a resolution of 0. 04 cm-1. Because of the multiple isotopomers present in the spectra, only 3 bands were rotationally analyzed. Perturbations were identified in two of these bands and all 3 transitions were found to terminate at the X1[sigma]+ ground electronic state. The electronic configurations that give rise to the observed states are discussed and molecular parameters for all of the analyzed bands are reported. Electronic spectra of the previously unobserved EuH and EuD molecules were studied by means of Fourier transform spectroscopy and laser-induced fluorescence. The extreme complexity of these transitions made rotational assignments of EuH bands impossible. However, the spin-spin interaction constant, [lambda], and Fermi contact parameter, bF, in the ground X9[sigma]- electronic state were estimated for the 151EuH and 153EuH isotopologues. Electronic spectra of SmH, SmCl, TmH and ErF molecules were recorded for the first time using Fourier transform spectrometer. The poor signal to noise ratio of the observed bands coupled with their complexity prevented a rotational analysis. The electronic states that may be involved in the observed transitions are discussed.

Relativistic many-body calculations of excitation energies, oscillator strengths, transition rates, and lifetimes in samarium like ions

NASA Astrophysics Data System (ADS)

Safronova, Ulyana; Safronova, Alla; Beiersdorfer, Peter

2013-05-01

Excitation energies, oscillator strengths, transition probabilities, and lifetimes are calculated for (5s2 + 5p2 + 5d2 + 5 s 5 d + 5 s 5 g + 5 p 5 f) - (5 s 5 p + 5 s 5 f + 5 p 5 d + 5 p 5 g) electric dipole transitions in Sm-like ions with nuclear charge Z ranging from 74 to 100. Relativistic many-body perturbation theory (RMBPT), including the Breit interaction, is used to evaluate retarded E1 matrix elements in length and velocity forms. The calculations start from a 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 Dirac-Fock potential. First-order perturbation theory is used to obtain intermediate coupling coefficients, and the second-order RMBPT is used to determine the matrix elements. The contributions from negative-energy states are included in the second-order E1 matrix elements to achieve agreement between length-form and velocity-form amplitudes. The resulting transition energies and transition probabilities, and lifetimes for Sm-like W12+ are compared with results obtained by the relativistic Hartree-Fock approximation (COWAN code) to estimate contribution of the 4 f -core-excited states. Trends of excitation energies and oscillator strengths as function of nuclear charge Z are shown graphically for selected states and transitions. This work provides a number of yet unmeasured properti. This research was sponsored by the grant DE-FG02-08ER54951.

Photoelectron spectrum of PrO{sup −}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kafader, Jared O.; Ray, Manisha; Jarrold, Caroline Chick

The photoelectron (PE) spectrum of PrO{sup −} exhibits a short 835 ± 20 cm{sup −1} vibrational progression of doublets (210 ± 30 cm{sup −1} splitting) assigned to transitions from the 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s}{sup 2} Ω = 4 anion ground state to the 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s} Ω = 3.5 and 4.5 neutral states. This assignment is analogous to that of the recently reported PE spectrum of CeO{sup −}, though the 82 cm{sup −1} splitting between the 4f [{sup 2}F{sub 2.5}] σ{sub 6s} Ω = 2 and Ω = 3 CeO neutral states couldmore » not be resolved [Ray et al., J. Chem. Phys. 142, 064305 (2015)]. The origin of the transition to the Ω = 3.5 neutral ground state is 0.96 ± 0.01 eV, which is the adiabatic electron affinity of PrO. Density functional theory calculations on the anion and neutral molecules support the assignment. The appearance of multiple, irregularly spaced and low-intensity features observed ca. 1 eV above the ground state cannot be reconciled with low-lying electronic states of PrO that are accessible via one-electron detachment. However, neutral states correlated with the 4f{sup 2} [{sup 3}H{sub 4}] 5d superconfiguration are predicted to be approximately 1 eV above the 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s} Ω = 3.5 neutral ground state, leading to the assignment of these features to shake-up transitions to the excited neutral states. Based on tentative hot band transition assignments, the term energy of the previously unobserved 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s} Ω = 2.5 neutral state is determined to be 1840 ± 110 cm{sup −1}.« less

Quantum Photonics Beyond Conventional Computing

DTIC Science & Technology

2015-07-10

polarisation using a half- wave plate (HWP), the two arms are combined by a polarising beam splitter (PBS). The resulting state is passed through the...phase-matched for Type-I SPDC, creating non -collinear degenerate horizontally polarised photon pairs at 808 nm. After converting one arm to vertical...For the case of non -interacting fermions, the transition probabilities for states under unitary evolution are governed by matrix determinants, which are

An equation-of-state-meter of quantum chromodynamics transition from deep learning.

PubMed

Pang, Long-Gang; Zhou, Kai; Su, Nan; Petersen, Hannah; Stöcker, Horst; Wang, Xin-Nian

2018-01-15

A primordial state of matter consisting of free quarks and gluons that existed in the early universe a few microseconds after the Big Bang is also expected to form in high-energy heavy-ion collisions. Determining the equation of state (EoS) of such a primordial matter is the ultimate goal of high-energy heavy-ion experiments. Here we use supervised learning with a deep convolutional neural network to identify the EoS employed in the relativistic hydrodynamic simulations of heavy ion collisions. High-level correlations of particle spectra in transverse momentum and azimuthal angle learned by the network act as an effective EoS-meter in deciphering the nature of the phase transition in quantum chromodynamics. Such EoS-meter is model-independent and insensitive to other simulation inputs including the initial conditions for hydrodynamic simulations.

Narrow-line laser cooling by adiabatic transfer

NASA Astrophysics Data System (ADS)

Norcia, Matthew A.; Cline, Julia R. K.; Bartolotta, John P.; Holland, Murray J.; Thompson, James K.

2018-02-01

We propose and demonstrate a novel laser cooling mechanism applicable to particles with narrow-linewidth optical transitions. By sweeping the frequency of counter-propagating laser beams in a sawtooth manner, we cause adiabatic transfer back and forth between the ground state and a long-lived optically excited state. The time-ordering of these adiabatic transfers is determined by Doppler shifts, which ensures that the associated photon recoils are in the opposite direction to the particle’s motion. This ultimately leads to a robust cooling mechanism capable of exerting large forces via a weak transition and with reduced reliance on spontaneous emission. We present a simple intuitive model for the resulting frictional force, and directly demonstrate its efficacy for increasing the total phase-space density of an atomic ensemble. We rely on both simulation and experimental studies using the 7.5 kHz linewidth 1S0 to 3P1 transition in 88Sr. The reduced reliance on spontaneous emission may allow this adiabatic sweep method to be a useful tool for cooling particles that lack closed cycling transitions, such as molecules.

Monte-Carlo simulations of the clean and disordered contact process in three space dimensions

NASA Astrophysics Data System (ADS)

Vojta, Thomas

2013-03-01

The absorbing-state transition in the three-dimensional contact process with and without quenched randomness is investigated by means of Monte-Carlo simulations. In the clean case, a reweighting technique is combined with a careful extrapolation of the data to infinite time to determine with high accuracy the critical behavior in the three-dimensional directed percolation universality class. In the presence of quenched spatial disorder, our data demonstrate that the absorbing-state transition is governed by an unconventional infinite-randomness critical point featuring activated dynamical scaling. The critical behavior of this transition does not depend on the disorder strength, i.e., it is universal. Close to the disordered critical point, the dynamics is characterized by the nonuniversal power laws typical of a Griffiths phase. We compare our findings to the results of other numerical methods, and we relate them to a general classification of phase transitions in disordered systems based on the rare region dimensionality. This work has been supported in part by the NSF under grants no. DMR-0906566 and DMR-1205803.

Modeling and visualizing cell type switching.

PubMed

Ghaffarizadeh, Ahmadreza; Podgorski, Gregory J; Flann, Nicholas S

2014-01-01

Understanding cellular differentiation is critical in explaining development and for taming diseases such as cancer. Differentiation is conventionally represented using bifurcating lineage trees. However, these lineage trees cannot readily capture or quantify all the types of transitions now known to occur between cell types, including transdifferentiation or differentiation off standard paths. This work introduces a new analysis and visualization technique that is capable of representing all possible transitions between cell states compactly, quantitatively, and intuitively. This method considers the regulatory network of transcription factors that control cell type determination and then performs an analysis of network dynamics to identify stable expression profiles and the potential cell types that they represent. A visualization tool called CellDiff3D creates an intuitive three-dimensional graph that shows the overall direction and probability of transitions between all pairs of cell types within a lineage. In this study, the influence of gene expression noise and mutational changes during myeloid cell differentiation are presented as a demonstration of the CellDiff3D technique, a new approach to quantify and envision all possible cell state transitions in any lineage network.

Disordered Kitaev chains with long-range pairing.

PubMed

Cai, Xiaoming

2017-03-22

We study the competition of disorder and superconductivity for a generalized Kitaev model in incommensurate potentials. The generalized Kitaev model describes one dimensional spinless fermions with long-range p-wave superconducting pairing, which decays with distance l as a power law  ∼[Formula: see text]. We focus on the transition from the topological superconducting phase to the topologically trivial Anderson localized phase, and effects of the exponent α on this phase transition. In the topological superconducting phase, for a system under open boundary condition the amplitude of zero-mode Majorana fermion has a hybrid exponential-algebraic decay as the distance increases from the edge. In the Anderson localized phase, some single-particle states remain critical for very strong disorders and the number of critical states increases as α decreases. In addition, except for critical disorders, the correlation function always has an exponential decay at the short range and an algebraic decay at the long range. Phase transition points are also numerically determined and the topological phase transition happens earlier at a smaller disorder strength for a system with smaller α.

Theoretical Investigation of the Electronic Structure of Fe(II) Complexes at Spin-State Transitions

PubMed Central

2013-01-01

The electronic structure relevant to low spin (LS)↔high spin (HS) transitions in Fe(II) coordination compounds with a FeN6 core are studied. The selected [Fe(tz)6]2+ (1) (tz = 1H-tetrazole), [Fe(bipy)3]2+ (2) (bipy = 2,2′-bipyridine), and [Fe(terpy)2]2+ (3) (terpy = 2,2′:6′,2″-terpyridine) complexes have been actively studied experimentally, and with their respective mono-, bi-, and tridentate ligands, they constitute a comprehensive set for theoretical case studies. The methods in this work include density functional theory (DFT), time-dependent DFT (TD-DFT), and multiconfigurational second order perturbation theory (CASPT2). We determine the structural parameters as well as the energy splitting of the LS–HS states (ΔEHL) applying the above methods and comparing their performance. We also determine the potential energy curves representing the ground and low-energy excited singlet, triplet, and quintet d6 states along the mode(s) that connect the LS and HS states. The results indicate that while DFT is well suited for the prediction of structural parameters, an accurate multiconfigurational approach is essential for the quantitative determination of ΔEHL. In addition, a good qualitative agreement is found between the TD-DFT and CASPT2 potential energy curves. Although the TD-DFT results might differ in some respect (in our case, we found a discrepancy at the triplet states), our results suggest that this approach, with due care, is very promising as an alternative for the very expensive CASPT2 method. Finally, the two-dimensional (2D) potential energy surfaces above the plane spanned by the two relevant configuration coordinates in [Fe(terpy)2]2+ were computed at both the DFT and CASPT2 levels. These 2D surfaces indicate that the singlet–triplet and triplet–quintet states are separated along different coordinates, i.e., different vibration modes. Our results confirm that in contrast to the case of complexes with mono- and bidentate ligands, the singlet–quintet transitions in [Fe(terpy)2]2+ cannot be described using a single configuration coordinate. PMID:25821416

Determining characteristics of artificial near-Earth objects using observability analysis

NASA Astrophysics Data System (ADS)

Friedman, Alex M.; Frueh, Carolin

2018-03-01

Observability analysis is a method for determining whether a chosen state of a system can be determined from the output or measurements. Knowledge of state information availability resulting from observability analysis leads to improved sensor tasking for observation of orbital debris and better control of active spacecraft. This research performs numerical observability analysis of artificial near-Earth objects. Analysis of linearization methods and state transition matrices is performed to determine the viability of applying linear observability methods to the nonlinear orbit problem. Furthermore, pre-whitening is implemented to reformulate classical observability analysis. In addition, the state in observability analysis is typically composed of position and velocity; however, including object characteristics beyond position and velocity can be crucial for precise orbit propagation. For example, solar radiation pressure has a significant impact on the orbit of high area-to-mass ratio objects in geosynchronous orbit. Therefore, determining the time required for solar radiation pressure parameters to become observable is important for understanding debris objects. In order to compare observability analysis results with and without measurement noise and an extended state, quantitative measures of observability are investigated and implemented.

Studies of singlet Rydberg series of LiH derived from Li(nl) + H(1s), with n ≤ 6 and l ≤ 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gim, Yeongrok; Department of Chemistry, Ajou University, Suwon 443-749; Lee, Chun-Woo, E-mail: clee@ajou.ac.kr

2014-10-14

The 50 singlet states of LiH composed of 49 Rydberg states and one non-Rydberg ionic state derivable from Li(nl) + H(1s), with n ≤ 6 and l ≤ 4, are studied using the multi-reference configuration interaction method combined with the Stuttgart/Köln group's effective core potential/core polarization potential method. Basis functions that can yield energy levels up to the 6g orbital of Li have been developed, and they are used with a huge number of universal Kaufmann basis functions for Rydberg states. The systematics and regularities of the physical properties such as potential energies, quantum defects, permanent dipole moments, transition dipolemore » moments, and nonadiabatic coupling matrix elements of the Rydberg series are studied. The behaviors of potential energy curves and quantum defect curves are explained using the Fermi approximation. The permanent dipole moments of the Rydberg series reveal that they are determined by the sizes of the Rydberg orbitals, which are proportional to n{sup 2}. Interesting mirror relationships of the dipole moments are observed between l-mixed Rydberg series, with the rule Δl = ±1, except for s–d mixing, which is also accompanied by n-mixing. The members of the l-mixed Rydberg series have dipole moments with opposite directions. The first derivatives of the dipole moment curves, which show the charge-transfer component, clearly show not only mirror relationships in terms of direction but also oscillations. The transition dipole moment matrix elements of the Rydberg series are determined by the small-r region, with two consequences. One is that the transition dipole moment matrix elements show n{sup −3/2} dependence. The other is that the magnitudes of the transition dipole moment matrix elements decrease rapidly as l increases.« less

Studies of singlet Rydberg series of LiH derived from Li(nl) + H(1s), with n ≤ 6 and l ≤ 4

NASA Astrophysics Data System (ADS)

Gim, Yeongrok; Lee, Chun-Woo

2014-10-01

The 50 singlet states of LiH composed of 49 Rydberg states and one non-Rydberg ionic state derivable from Li(nl) + H(1s), with n ≤ 6 and l ≤ 4, are studied using the multi-reference configuration interaction method combined with the Stuttgart/Köln group's effective core potential/core polarization potential method. Basis functions that can yield energy levels up to the 6g orbital of Li have been developed, and they are used with a huge number of universal Kaufmann basis functions for Rydberg states. The systematics and regularities of the physical properties such as potential energies, quantum defects, permanent dipole moments, transition dipole moments, and nonadiabatic coupling matrix elements of the Rydberg series are studied. The behaviors of potential energy curves and quantum defect curves are explained using the Fermi approximation. The permanent dipole moments of the Rydberg series reveal that they are determined by the sizes of the Rydberg orbitals, which are proportional to n2. Interesting mirror relationships of the dipole moments are observed between l-mixed Rydberg series, with the rule Δl = ±1, except for s-d mixing, which is also accompanied by n-mixing. The members of the l-mixed Rydberg series have dipole moments with opposite directions. The first derivatives of the dipole moment curves, which show the charge-transfer component, clearly show not only mirror relationships in terms of direction but also oscillations. The transition dipole moment matrix elements of the Rydberg series are determined by the small-r region, with two consequences. One is that the transition dipole moment matrix elements show n-3/2 dependence. The other is that the magnitudes of the transition dipole moment matrix elements decrease rapidly as l increases.

Kinetics of (2 × 4) → (3 × 1(6)) structural changes on GaAs(001) surfaces during the UHV annealing

NASA Astrophysics Data System (ADS)

Vasev, A. V.; Putyato, M. A.; Preobrazhenskii, V. V.

2018-06-01

The peculiarities of superstructural transition (2 × 4) → (3 × 1(6)) on the GaAs(001) surface were studied by the RHEED method in the conditions initiated by a sharp change of the arsenic flux. The specular beam intensities RHEED picture dependences on time were obtained during the transition. The measurement results were analyzed within the JMAK (Johnson - Melh - Avrami - Kolmogorov) kinetic model. It was established that the process of structural rearrangement proceeds in two stages and it is realized through the state of intermediate disordering, domains with different reconstructions being coexistent on the surface. The activation energies and phase transition velocities were determined for each of the stages. The procedure for precise determination of GaAs(001) surface temperature using the features of the α(2 × 4) → DO transition process kinetic was proposed. The results of this work allow us to broaden our understanding of the reconstruction transitions mechanisms. This information has a key (fundamental and applied) nature for the technologies of epitaxial growth of multilayer heterostructures, where the interface planarity and the sharpness of composition profile are of particular importance.

A review of the role of the California Transportation Commission in public transportation in California

DOT National Transportation Integrated Search

1986-08-05

Reports findings and recommendations of, and responses to,the California Transportation Commission's study to determine and document the focus of the CTC in transit, and more broadly, public transportation, activities in the State of California.

Making certain progress in uncertain times : the Transportation Research Board's 2008 Field Visit Program

DOT National Transportation Integrated Search

2009-01-01

Each year, TRBs Technical Activities Division staff visit state departments of transportation, as well as selected universities, transit and other modal agencies, and industry organizations, to determine the issues they are facing and how TRB can ...

In-Beam Studies of High-Spin States in Mercury -183 and MERCURY-181

NASA Astrophysics Data System (ADS)

Shi, Detang

The high-spin states of ^{183 }Hg were studied by using the reaction ^{155}Gd(^{32}S, 4n)^{183}Hg at a beam energy of 160 MeV with the tandem-linac accelerator system and the multi-element gamma-ray detection array at Florida State University. Two new bands, consisting of stretched E2 transitions and connected by M1 inter-band transitions, were identified in ^{183}Hg. Several new levels were added to the previously known bands at higher spin. The spins and parities to the levels in ^{183}Hg were determined from the analysis of their DCO ratios and B(M1)/B(E2) ratios. While the two pairs of previously known bands in ^ {183}Hg were proposed to 7/2^ -[514] and 9/2^+ [624], the two new bands are assigned as the 1/2^-[521] ground state configuration based upon the systematics of Nilsson orbitals in this mass region. The 354-keV transition previously was considered to be an E2 transition and assigned as the only transition from a band which is built on an oblate deformed i_{13/2} isomeric state. However, our DCO ratio analysis indicates that the 354-keV gamma-ray is an M1 transition. This changes the decay pattern of the 9/2^+[624 ] prolate structure in ^ {183}Hg, so it is seen to feed only into the i_{13/2} isomer band head. Our knowledge of the mercury nuclei far from stability was then extended through an in-beam study of the reaction ^{144}Sm(^{40 }Ar, 3n)^{181}Hg by using the Fragment Mass Analyzer (FMA) and the ten-Compton-suppressed -germanium-detector system at Argonne National Laboratory. Band structures to high-spin states are established for the first time in ^{181}Hg in the present experiment. The observed level structure of ^{181}Hg is midway between those in ^{185}Hg and in ^{183}Hg. The experimental results are analyzed in the framework of the cranking shell model (CSM). Alternative theoretical explanations are also presented and discussed. Systematics of neighboring mercury isotopes and N = 103 isotones is analyzed.

The structure of Al-23 and astrophysical consequences

NASA Astrophysics Data System (ADS)

Zhai, Yongjun

Motivated by existing nuclear astrophysics problems, the b-decay of the proton rich nucleus 23 Al was studied for the first time with pure samples which were obtained by using the 1 H( 24 Mg, 23 Al)2n reaction and the MARS recoil separator at Texas A&M University. b and b-g coincidence measurements were made with a fast tape-transport system, scintillator, BGO and HPGe g detectors. The experiment allowed us to measure absolute b branching ratios and to determine log ft values for transitions to final states in 23 Mg, including the isobaric analog state (IAS), and, therefore, to determine unambiguously the spin and parity of the 23 Al ground state to be J p = 5/2 + . This work excludes the large increases in the radiative proton capture cross section for the reaction 22 Mg(p,g) 23 Al at astrophysical energies, which were implied by claims that the spin and parity of the 23 Al ground state were J p = 1/2 + . More precise half life and mass determinations of 23 Al were obtained from the experimental data. The log ft for the Fermi transition to its isobaric analog state in 23 Mg was also determined for the first time. This IAS and a state 16 keV below it were observed, well separated in the same experiment for the first time. The b- decay scheme of the proton rich nucleus 23 Al was established. We can now solve a number of inconsistencies in the literature, exclude strong isospin mixing claimed before, and obtain a new determination of the resonance strength. The IAS and the state 16 keV below it are resonances in the 22 Na(p,g) 23 Mg reaction at energies that are important in novae. This second state turns out to be the resonance that gives the most important contribution in the depletion of 22Na from novae. Both of the reactions of 22 Mg(p,g) 23 Al and 22 Na(p,g) 23 Mg have been suggested as possible candidates for diverting some of the flux in oxygen-neon novae explosions from the A=22 into the A=23 mass chain.

Enriching mission planning approach with state transition graph heuristics for deep space exploration

NASA Astrophysics Data System (ADS)

Jin, Hao; Xu, Rui; Xu, Wenming; Cui, Pingyuan; Zhu, Shengying

2017-10-01

As to support the mission of Mars exploration in China, automated mission planning is required to enhance security and robustness of deep space probe. Deep space mission planning requires modeling of complex operations constraints and focus on the temporal state transitions of involved subsystems. Also, state transitions are ubiquitous in physical systems, but have been elusive for knowledge description. We introduce a modeling approach to cope with these difficulties that takes state transitions into consideration. The key technique we build on is the notion of extended states and state transition graphs. Furthermore, a heuristics that based on state transition graphs is proposed to avoid redundant work. Finally, we run comprehensive experiments on selected domains and our techniques present an excellent performance.

Origin of the transition voltage in gold-vacuum-gold atomic junctions.

PubMed

Wu, Kunlin; Bai, Meilin; Sanvito, Stefano; Hou, Shimin

2013-01-18

The origin and the distance dependence of the transition voltage of gold-vacuum-gold junctions are investigated by employing first-principles quantum transport simulations. Our calculations show that atomic protrusions always exist on the electrode surface of gold-vacuum-gold junctions fabricated using the mechanically controllable break junction (MCBJ) method. The transition voltage of these gold-vacuum-gold junctions with atomically sharp electrodes is determined by the local density of states (LDOS) of the apex gold atom on the electrode surface rather than by the vacuum barrier shape. More specifically, the absolute value of the transition voltage roughly equals the rising edge of the LDOS peak contributed by the 6p atomic orbitals of the gold atoms protruding from the electrode surface, whose local Fermi level is shifted downwards when a bias voltage is applied. Since the LDOS of the apex gold atom depends strongly on the exact shape of the electrode, the transition voltage is sensitive to the variation of the atomic configuration of the junction. For asymmetric junctions, the transition voltage may also change significantly depending on the bias polarity. Considering that the occurrence of the transition voltage requires the electrode distance to be larger than a critical value, the interaction between the two electrodes is actually rather weak. Consequently, the LDOS of the apex gold atom is mainly determined by its local atomic configuration and the transition voltage only depends weakly on the electrode distance as observed in the MCBJ experiments.

Dynamic phase diagram of a nonionic surfactant lamellar phase.

PubMed

Gentile, Luigi; Behrens, Manja A; Balog, Sandor; Mortensen, Kell; Ranieri, Giuseppe A; Olsson, Ulf

2014-04-03

The dynamic phase diagram of triethylene glycol dodecyl ether (C12E3) in D2O was determined for 40, 50, and 60 wt % of surfactant. The shear flow effect on the nonionic lamellar phase was investigated as a function of temperature and concentration. The transition from planar lamellae (Lα)-to-multilamellar vesicles (MLVs) was characterized by means of rheology, rheo-small-angle neutron and light scattering. New insight into the nature of the transition region between Lα and the MLVs state is provided. A disorder-order transition was also observed by SANS. This is attributed to a transition from disordered MLVs to a close-packed array of MLV's with slightly higher order than before. Moreover flow instability was observed in the shear-thickening regime at 40 °C.

Thermomagnetic phenomena in the mixed state of high temperature superconductors

NASA Technical Reports Server (NTRS)

Meilikhov, E. Z.

1995-01-01

Galvano- and thermomagnetic-phenomena in high temperature superconductors, based on kinetic coefficients, are discussed, along with a connection between the electric field and the heat flow in superconductor mixed state. The relationship that determines the transport coefficients of high temperature superconductors in the mixed state based on Seebeck and Nernst effects is developed. It is shown that this relationship is true for a whole transition region of the resistive mixed state of a superconductor. Peltier, Ettingshausen and Righi-Leduc effects associated with heat conductivity as related to high temperature superconductors are also addressed.

An inhibitory gate for state transition in cortex

PubMed Central

Zucca, Stefano; D’Urso, Giulia; Pasquale, Valentina; Vecchia, Dania; Pica, Giuseppe; Bovetti, Serena; Moretti, Claudio; Varani, Stefano; Molano-Mazón, Manuel; Chiappalone, Michela; Panzeri, Stefano; Fellin, Tommaso

2017-01-01

Large scale transitions between active (up) and silent (down) states during quiet wakefulness or NREM sleep regulate fundamental cortical functions and are known to involve both excitatory and inhibitory cells. However, if and how inhibition regulates these activity transitions is unclear. Using fluorescence-targeted electrophysiological recording and cell-specific optogenetic manipulation in both anesthetized and non-anesthetized mice, we found that two major classes of interneurons, the parvalbumin and the somatostatin positive cells, tightly control both up-to-down and down-to-up state transitions. Inhibitory regulation of state transition was observed under both natural and optogenetically-evoked conditions. Moreover, perturbative optogenetic experiments revealed that the inhibitory control of state transition was interneuron-type specific. Finally, local manipulation of small ensembles of interneurons affected cortical populations millimetres away from the modulated region. Together, these results demonstrate that inhibition potently gates transitions between cortical activity states, and reveal the cellular mechanisms by which local inhibitory microcircuits regulate state transitions at the mesoscale. DOI: http://dx.doi.org/10.7554/eLife.26177.001 PMID:28509666

A modified PATH algorithm rapidly generates transition states comparable to those found by other well established algorithms

PubMed Central

Chandrasekaran, Srinivas Niranj; Das, Jhuma; Dokholyan, Nikolay V.; Carter, Charles W.

2016-01-01

PATH rapidly computes a path and a transition state between crystal structures by minimizing the Onsager-Machlup action. It requires input parameters whose range of values can generate different transition-state structures that cannot be uniquely compared with those generated by other methods. We outline modifications to estimate these input parameters to circumvent these difficulties and validate the PATH transition states by showing consistency between transition-states derived by different algorithms for unrelated protein systems. Although functional protein conformational change trajectories are to a degree stochastic, they nonetheless pass through a well-defined transition state whose detailed structural properties can rapidly be identified using PATH. PMID:26958584

CRDS of 17O enriched water between 5850 and 6671 cm-1: More than 1000 energy levels of H217O and HD17O newly determined

NASA Astrophysics Data System (ADS)

Mikhailenko, S. N.; Leshchishina, O.; Karlovets, E. V.; Mondelain, D.; Kassi, S.; Campargue, A.

2016-07-01

The room temperature absorption spectrum of water vapor highly enriched in 17O has been recorded by Cavity Ring Down Spectroscopy (CRDS) between 5850 and 6671 cm-1. Two series of recordings were performed with pressure values of 1.0 and 12.0 Torr. The investigated spectral region corresponds to the important 1.55 μm transparency window of the atmosphere where water absorption is very weak. The high sensitivity of the recordings (αmin 5×10-11 cm-1) allows detecting lines with intensity spanning six orders of magnitude (1.4×10-30-3.6×10-24 cm/molecule at room temperature). The experimental list includes more than 10,300 lines. The assignments of water lines were performed using known experimental energy levels as well as calculated line lists based on the results of Partridge and Schwenke. More than 8500 lines were assigned to 9619 transitions of six water isotopologues (H216O, H217O, H218O, HD16O, HD17O and HD18O). All but four transitions of the 16O and 18O isotopologues were assigned using known experimental energy levels. More than half of the assigned H217O and HD17O transitions correspond to new (or corrected) upper energy levels. About 1000 new H217O transitions associated with upper states of the second triad and of the first hexad were identified. Most of the newly assigned HD17O transitions belong to the ν1+ν3 and 2ν2+ν3 bands. The assigned transitions allowed to newly determine or correct 20 highly excited rotational levels of the vibrational ground state of this isotopologue. Overall 791 and 266 energy levels are newly determined for H217O and HD17O, respectively. A few additional levels were corrected compared to literature values. The obtained experimental results are compared to the spectroscopic parameters provided by the HITRAN database and to the empirical energy levels recommended by an IUPAC task group.

Control of the orientation and photoinduced phase transitions of macrocyclic azobenzene.

PubMed

Uchida, Emi; Sakaki, Kouji; Nakamura, Yumiko; Azumi, Reiko; Hirai, Yuki; Akiyama, Haruhisa; Yoshida, Masaru; Norikane, Yasuo

2013-12-16

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups (1) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal-isotropic phase-crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be -0.84. Heating enhances the thermal cis-to-trans isomerization and subsequent cooling returned crystals of the trans/trans isomer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectra of 42S1/2→32D5/2 Transitions of a Single Trapped 40Ca+ Ion

NASA Astrophysics Data System (ADS)

Gong, Shi-Jie; Zhou, Fei; Wu, Hao-Yu; Wan, Wei; Chen, Liang; Feng, Mang

2015-01-01

We investigate the spectra of the electric quadrupole 42S1/2→32D5/2 transitions in a single 40Ca+ ion confined in a home-built linear trap. We probe the transitions with an ultra-narrow bandwidth laser at 729 nm. In a weak magnetic field, the quadrupole transition splits into ten components with the maximal line strength proportional to their squared Clebsch—Gordan factors. In a magnetic field of the order of Gauss, the observed equidistant sideband reflects the Zeeman substructure modulated by the quantized oscillation due to the secular motion in the trap. The temperature of the trapped ion can be determined by the envelope of the sideband spectrum. We also demonstrate the Rabi oscillation in a carrier transition after the ion has been Doppler cooled, which can be fitted by the model with the thermal state of motion.

Thermodynamic and kinetic theory of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets on soluble particles.

PubMed

Shchekin, Alexander K; Shabaev, Ilya V; Hellmuth, Olaf

2013-02-07

Thermodynamic and kinetic peculiarities of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets formed on soluble condensation nuclei from a solvent vapor have been considered. The interplay of the effects of solubility and the size of condensation nuclei has been analyzed. Activation barriers for the deliquescence and phase transitions and for the reverse efflorescence transition have been determined as functions of the relative humidity of the vapor-gas atmosphere, initial size, and solubility of condensation nuclei. It has been demonstrated that, upon variations in the relative humidity of the atmosphere, the crossover in thermodynamically stable and unstable variables of the droplet state takes place. The physical meaning of stable and unstable variables has been clarified. The kinetic equations for establishing equilibrium and steady distributions of binary droplets have been solved. The specific times for relaxation, deliquescence and efflorescence transitions have been calculated.

Determination of anisotropic dipole moments in self-assembled quantum dots using Rabi oscillations

NASA Astrophysics Data System (ADS)

Muller, A.; Wang, Q. Q.; Bianucci, P.; Shih, C. K.; Xue, Q. K.

2004-02-01

By investigating the polarization-dependent Rabi oscillations using photoluminescence spectroscopy, we determined the respective transition dipole moments of the two excited excitonic states |Ex> and |Ey> of a single self-assembled quantum dot that are nondegenerate due to shape anisotropy. We find that the ratio of the two dipole moments is close to the physical elongation ratio of the quantum dot.

Cross section measurement of 14N(p ,γ )15O in the CNO cycle

NASA Astrophysics Data System (ADS)

Li, Q.; Görres, J.; deBoer, R. J.; Imbriani, G.; Best, A.; Kontos, A.; LeBlanc, P. J.; Uberseder, E.; Wiescher, M.

2016-05-01

Background: The CNO cycle is the main energy source in stars more massive than our sun; it defines the energy production and the cycle time that lead to the lifetime of massive stars, and it is an important tool for the determination of the age of globular clusters. In our sun about 1.6% of the total solar neutrino flux comes from the CNO cycle. The largest uncertainty in the prediction of this CNO flux from the standard solar model comes from the uncertainty in the 14N(p ,γ )15O reaction rate; thus, the determination of the cross section at astrophysical temperatures is of great interest. Purpose: The total cross section of the 14N(p ,γ )15O reaction has large contributions from the transitions to the Ex=6.79 MeV excited state and the ground state of 15O. The Ex=6.79 MeV transition is dominated by radiative direct capture, while the ground state is a complex mixture of direct and resonance capture components and the interferences between them. Recent studies have concentrated on cross-section measurements at very low energies, but broad resonances at higher energy may also play a role. A single measurement has been made that covers a broad higher-energy range but it has large uncertainties stemming from uncorrected summing effects. Furthermore, the extrapolations of the cross section vary significantly depending on the data sets considered. Thus, new direct measurements have been made to improve the previous high-energy studies and to better constrain the extrapolation. Methods: Measurements were performed at the low-energy accelerator facilities of the nuclear science laboratory at the University of Notre Dame. The cross section was measured over the proton energy range from Ep=0.7 to 3.6 MeV for both the ground state and the Ex=6.79 MeV transitions at θlab=0∘ , 45∘, 90∘, 135∘, and 150∘. Both TiN and implanted-14N targets were utilized. γ rays were detected by using an array of high-purity germanium detectors. Results: The excitation function as well as angular distributions of the two transitions were measured. A multichannel R -matrix analysis was performed with the present data and is compared with previous measurements. The analysis covers a wide energy range so that the contributions from broad resonances and direct capture can be better constrained. Conclusion: The astrophysical S factors of the Ex=6.79 MeV and the ground-state transitions were extrapolated to low energies with the newly measured differential-cross-section data. Based on the present work, the extrapolations yield S6.79(0 ) =1.29 ±0.04 (stat ) ±0.09 (syst ) keV b and Sg.s.(0 ) =0.42 ±0.04 (stat ) keV b . While significant improvement and consistency is found in modeling the Ex=6.79 MeV transition, large inconsistencies in both the R -matrix fitting and the low-energy data are reaffirmed for the ground-state transition. Reflecting this, a systematic uncertainty of -0.19+0.09keV b is recommended for the ground-state transition.

The Microwave Spectroscopy of Aminoacetonitrile in the Vibrational Excited States 2

NASA Astrophysics Data System (ADS)

Fujita, Chiho; Higurashi, Haruka; Ozeki, Hiroyuki; Kobayashi, Kaori

2016-06-01

Aminoacetonitrile (NH_2CH_2CN) is a potential precursor of the simplest amino acid, glycine in the interstellar space and was detected toward SgrB2(N). We have extended measurements up to 1.3 THz so that the strongest transitions that may be found in the terahertz region should be covered. Aminoacetonitrile has a few low-lying vibrational excited states and indeed the pure rotational transitions in these vibrational excited states were found. The pure rotational transitions in six vibrational excited states in the 80-180 GHz range have been assigned and centrifugal distortion constants up to the sextic terms were determined. Based on spectral intensities and the vibrational information from Bak et al., They were assigned to the 3 low-lying fundamentals, 1 overtone and 2 combination bands. In the submillimeter wavelength region, perturbations were recognized and some of the lines were off by more than a few MHz. At this moment, these perturbed transitions are not included in our analysis. A. Belloche, K. M. Menten, C. Comito, H. S. P. Müller, P. Schilke, J. Ott, S. Thorwirth, and C. Hieret, 2008, Astronom. & Astrophys. 482, 179 (2008). Y. Motoki, Y. Tsunoda, H. Ozeki, and K. Kobayashi, Astrophys. J. Suppl. Ser. 209, 23 (2013). B. Bak, E. L. Hansen, F. M. Nicolaisen, and O. F. Nielsen, Can. J. Phys. 53, 2183 (1975) C. Fujita, H. Ozeki, and K. Kobayashi, 70th International Symposium on Molecular Spectroscopy (2015), MH14.

Microscopic description of triaxiality in Ru isotopes with covariant energy density functional theory

NASA Astrophysics Data System (ADS)

Shi, Z.; Li, Z. P.

2018-03-01

Background: Triaxiality in nuclear low-lying states has attracted great interest for many years. Recently, reduced transition probabilities for levels near the ground state in 110Ru have been measured and provided strong evidence of a triaxial shape of this nucleus. Purpose: The aim of this work is to provide a microscopic study of low-lying states for Ru isotopes with A ≈100 and to examine in detail the role of triaxiality and the evolution of quadrupole shapes with the isospin and spin degrees of freedom. Method: Low-lying excitation spectra and transition probabilities of even-even Ru isotopes are described at the beyond-mean-field level by solving a five-dimensional collective Hamiltonian with parameters determined by constrained self-consistent mean-field calculations based on the relativistic energy density functional PC-PK1. Results: The calculated energy surfaces, low-energy spectra, and intraband and interband transition rates, as well as some characteristic collective observables, such as E (4g.s . +) /E (2g.s . +) ,E (2γ+) /E (4g.s . +) , and B (E 2 ;2g.s . +→0g.s . +) and γ -band staggerings, are in good agreement with the available experimental data. Conclusions: The main features of the experimental low-lying excitation spectra and electric transition rates are well reproduced and, thus, strongly support the onset of triaxiality in the low-lying excited states of Ru isotopes around 110Ru.

Telecommunications Policy Research Conference. Capital Recovery Section. Papers.

ERIC Educational Resources Information Center

Telecommunications Policy Research Conference, Inc., Washington, DC.

Two papers consider the capital recovery difficulties of telephone companies in the current deregulatory environment. The first, "Capital Recovery in the Transition Period" (Gail Garfield Schwartz, New York State Public Service Commission) describes the process determining depreciation in both regulated and deregulated environments, and…

42 CFR 433.50 - Basis, scope, and applicability.

Code of Federal Regulations, 2014 CFR

2014-10-01

... participation in expenditures for medical assistance. (2) Defines provider-related donations and health care... treatment of revenues from provider-related donations and health care-related taxes in determining a State's... from provider-related donations and health care-related taxes during a transition period. (4...

An experimental and theoretical study of the A˜ 2A″Π -X˜ 2A' band system of the jet-cooled HBBr/DBBr free radical

NASA Astrophysics Data System (ADS)

Gharaibeh, Mohammed; Clouthier, Dennis J.; Tarroni, Riccardo

2016-06-01

The electronic spectra of the HBBr and DBBr free radicals have been studied in depth. These species were prepared in a pulsed electric discharge jet using a precursor mixture of BBr3 vapor and H2 or D2 in high pressure argon. Transitions to the electronic excited state of the jet-cooled radicals were probed with laser-induced fluorescence and the ground state energy levels were measured from the single vibronic level emission spectra. HBBr has an extensive band system in the red which involves a linear-bent transition between the two Renner-Teller components of what would be a 2Π state at linearity. We have used high level ab initio theory to calculate potential energy surfaces for the bent 2A' ground state and the linear A˜ 2A″Π excited state and we have determined the ro-vibronic energy levels variationally, including spin orbit effects. The correspondence between the computed and experimentally observed transition frequencies, upper state level symmetries, and H and B isotope shifts was used to make reliable assignments. We have shown that the ground state barriers to linearity, which range from 10 000 cm-1 in HBF to 2700 cm-1 in BH2, are inversely related to the energy of the first excited 2Σ (2A') electronic state. This suggests that a vibronic coupling mechanism is responsible for the nonlinear equilibrium geometries of the ground states of the HBX free radicals.

Localization of electrons and excitations

NASA Astrophysics Data System (ADS)

Larsson, Sven

2006-07-01

Electrons, electron holes, or excitations in finite or infinite 'multimer systems' may be localized or delocalized. In the theory of Hush, localization depends on the ratio Δ/ λ ( Δ/2 = coupling; λ = reorganization energy). The latter theory has been extended to the infinite system [S. Larsson, A. Klimkāns, Mol. Cryst. Liq. Cryst. 355 (2000) 217]. The metal/insulator transition often takes place abruptly as a function of Δ/ λ. It is argued that localization in a system with un-filled bands cannot be determined on the basis of Mott-Hubbard U alone, but depends on the number of accessible valence states, reorganization energy λ and coupling Δ (=2t). In fact U = 0 does not necessarily imply delocalization. The analysis here shows that there are many different situations for an insulator to metal transition. Charge transfer in doped NiO is characterized by Ni 2+ - Ni 3+ exchange while charge transfer in pure NiO is characterized by a disproportionation 2Ni 2+ → Ni + + Ni 3+. In spite of the great differences between these two cases, U has been applied without discrimination to both. The relevant localization parameters appear to be Δ and λ in the first case, with only two oxidation states, and U, Δ and λ in the second case with three oxidation states. The analysis is extended to insulator-metal transitions, giant magnetic resistance (GMR) and high Tc superconductivity (SC). λ and Δ can be determined quite accurately in quantum mechanical calculations involving only one and two monomers, respectively.

α decay of the T = 1 ,   2 + state in B 10 and isospin symmetry breaking in the A = 10 triplet

DOE PAGES

Kuvin, S. A.; Wuosmaa, A. H.; Lister, C. J.; ...

2017-10-03

Here, the rate of the T=1, 2+ to T=1, 0 + transition in 10B ( T=1, T z=0) is compared to the analog transitions in 10Be ( T=1, T z=–1) and 10C ( T=1, T z=+1) to provide constraints on ab initio calculations using realistic nuclear forces. The relevant state in 10B, at E x=5.164 MeV, is particle unbound. Therefore, a determination of the B( E2) electromagnetic transition rate requires a precise and accurate determination of the width of the state, as well as the α-particle and γ-ray branching ratios. Previous measurements of the α-particle branching ratio are just barelymore » in agreement. We report on a new study of the α-particle branch by studying the 10B(p,p') 10B* reaction in inverse kinematics with the HELIOS spectrometer. The α-particle branching ratio that we observe, 0.144±0.027, is in good agreement with the evaluated value and improves the associated uncertainty. The resulting experimental B( E2) value is 7.0±2.2 e 2fm 4 and is more consistent with a flat trend across the A=10 triplet than previously reported. This is inconsistent with Green's function Monte Carlo predictions using realistic three-nucleon Hamiltonians, which overpredict the B(E2) value in 10C and 10B.« less

Kinetic and thermodynamic acidities of substituted 1-benzyl-1-methoxy-2-nitroethylenes. Strong reduction of the transition state imbalance compared to other nitroalkanes.

PubMed

Bernasconi, Claude F; Ali, Mahammad; Gunter, Janette C

2003-01-08

Acidity constants of six substituted 1-benzyl-1-methoxy-2-nitroethylenes (2-Z with Z = m-NO(2), m-CF(3), m-Cl, H, p-Me, p-MeO) and their respective nitronic acids were determined in 50% DMSO-50% water (v/v) at 20 degrees C. Kinetic data were obtained on the reversible deprotonation of all six 2-Z by OH(-) and piperidine and on the reversible deprotonation of 2-NO(2)() by piperazine, 1-(2-hydroxyethyl)piperazine, and morpholine in the same solvent. These data allowed a determination of the Brønsted coefficients alpha (dependence on acidity of 2-Z) and beta (dependence on amine basicity). The fact that alpha > beta indicates the presence of a transition state imbalance which, however, is much smaller than that for the deprotonation of arylnitromethanes. The reasons for this reduction in the imbalance and their relevance to a recent study of the deprotonation of Fischer carbene complexes are discussed.

Discovering sparse transcription factor codes for cell states and state transitions during development

PubMed Central

Furchtgott, Leon A; Melton, Samuel; Menon, Vilas; Ramanathan, Sharad

2017-01-01

Computational analysis of gene expression to determine both the sequence of lineage choices made by multipotent cells and to identify the genes influencing these decisions is challenging. Here we discover a pattern in the expression levels of a sparse subset of genes among cell types in B- and T-cell developmental lineages that correlates with developmental topologies. We develop a statistical framework using this pattern to simultaneously infer lineage transitions and the genes that determine these relationships. We use this technique to reconstruct the early hematopoietic and intestinal developmental trees. We extend this framework to analyze single-cell RNA-seq data from early human cortical development, inferring a neocortical-hindbrain split in early progenitor cells and the key genes that could control this lineage decision. Our work allows us to simultaneously infer both the identity and lineage of cell types as well as a small set of key genes whose expression patterns reflect these relationships. DOI: http://dx.doi.org/10.7554/eLife.20488.001 PMID:28296636

Proximity-induced magnetism in transition-metal substituted graphene

DOE PAGES

Crook, Charles B.; Constantin, Costel; Ahmed, Towfiq; ...

2015-08-03

We investigate the interactions between two identical magnetic impurities substituted into a graphene superlattice. Using a first-principles approach, we calculate the electronic and magnetic properties for transition-metal substituted graphene systems with varying spatial separation. These calculations are compared for three different magnetic impurities, manganese, chromium, and vanadium. We determine the electronic band structure, density of states, and Millikan populations (magnetic moment) for each atom, as well as calculate the exchange parameter between the two magnetic atoms as a function of spatial separation. We find that the presence of magnetic impurities establishes a distinct magnetic moment in the graphene lattice, wheremore » the interactions are highly dependent on the spatial and magnetic characteristic between the magnetic and carbon atoms, which leads to either ferromagnetic or antiferromagnetic behavior. Furthermore, through an analysis of the calculated exchange energies and partial density of states, it is determined that interactions between the magnetic atoms can be classified as an RKKY interaction.« less

Coverage criteria for test case generation using UML state chart diagram

NASA Astrophysics Data System (ADS)

Salman, Yasir Dawood; Hashim, Nor Laily; Rejab, Mawarny Md; Romli, Rohaida; Mohd, Haslina

2017-10-01

To improve the effectiveness of test data generation during the software test, many studies have focused on the automation of test data generation from UML diagrams. One of these diagrams is the UML state chart diagram. Test cases are generally evaluated according to coverage criteria. However, combinations of multiple criteria are required to achieve better coverage. Different studies used various number and types of coverage criteria in their methods and approaches. The objective of this paper to propose suitable coverage criteria for test case generation using UML state chart diagram especially in handling loops. In order to achieve this objective, this work reviewed previous studies to present the most practical coverage criteria combinations, including all-states, all-transitions, all-transition-pairs, and all-loop-free-paths coverage. Calculation to determine the coverage percentage of the proposed coverage criteria were presented together with an example has they are applied on a UML state chart diagram. This finding would be beneficial in the area of test case generating especially in handling loops in UML state chart diagram.

Recoil ions from the β decay of 134Sb confined in a Paul trap

NASA Astrophysics Data System (ADS)

Siegl, K.; Scielzo, N. D.; Czeszumska, A.; Clark, J. A.; Savard, G.; Aprahamian, A.; Caldwell, S. A.; Alan, B. S.; Burkey, M. T.; Chiara, C. J.; Greene, J. P.; Harker, J.; Marley, S. T.; Morgan, G. E.; Munson, J. M.; Norman, E. B.; Orford, R.; Padgett, S.; Galván, A. Perez; Sharma, K. S.; Strauss, S. Y.

2018-03-01

The low-energy recoiling ions from the β decay of 134Sb were studied by using the Beta-decay Paul Trap. Using this apparatus, singly charged ions were suspended in vacuum at the center of a detector array used to detect emitted β particles, γ rays, and recoil ions in coincidence. The recoil ions emerge from the trap with negligible scattering, allowing β -decay properties and the charge-state distribution of the daughter ions to be determined from the β -ion coincidences. First-forbidden β -decay theory predicts a β -ν correlation coefficient of nearly unity for the 0- to 0+ transition from the ground state of 134Sb to the ground state of 134Te. Although this transition was expected to have a nearly 100% branching ratio, an additional 17.2(52)% of the β -decay strength must populate high-lying excited states to obtain an angular correlation consistent with unity. The extracted charge-state distribution of the recoiling ions was compared with existing β -decay results and the average charge state was found to be consistent with the results from lighter nuclei.

Analysis of the Rotational Structure of ˜{B}^2A' ← ˜{X}^2A' Transition of Isopropoxy Radical: Isolated State vs. Coupled States Model

NASA Astrophysics Data System (ADS)

Melnik, Dmitry G.; Miller, Terry A.; Liu, Jinjun

2013-06-01

Isopropoxy radicals are reactive intermediates in atmospheric and combustion chemistry. From the theoretical point of view, they represent an extreme case of ``isotopically'' substituted methoxy radicals with two methyl groups playing the role of heavy hydrogen isotopes. Previously the rotationally resolved spectra of ˜{B}^2A' ← ˜{X}^2A' electronic transition were successfully analyzed using a simple effective rotational Hamiltonian of the isolated ˜{X} and ˜{B} states. However, a number of the experimentally determined parameters appeared dramatically inconsistent with the quantum chemistry calculations and theoretical predictions based on the symmetry arguments. Recently, we analyzed these spectra using a coupled two state model, which explicitly includes interactions between the ground ˜{X}^2A' state and low-lying excited ˜{A}^2A^'' state. In this presentation we will discuss the results of this analysis and compare the parameters of both models and their physical significance. D. G. Melnik, T. A. Miller and J. Liu, TI15, 67^{th Molecular Spectroscopy Symposium}, Columbus, 2012

Pressure dependence of the photocycle kinetics of bacteriorhodopsin.

PubMed Central

Klink, B U; Winter, R; Engelhard, M; Chizhov, I

2002-01-01

The pressure dependence of the photocycle kinetics of bacteriorhodopsin from Halobacterium salinarium was investigated at pressures up to 4 kbar at 25 degrees C and 40 degrees C. The kinetics can be adequately modeled by nine apparent rate constants, which are assigned to irreversible transitions of a single relaxation chain of nine kinetically distinguishable states P(1) to P(9). All states except P(1) and P(9) consist of two or more spectral components. The kinetic states P(2) to P(6) comprise only the two fast equilibrating spectral states L and M. From the pressure dependence, the volume differences DeltaV(o)(LM) between these two spectral states could be determined that range from DeltaV(o)(LM) = -11.4 +/- 0.7 ml/mol (P(2)) to DeltaV(o)(LM) = 14.6 +/- 2.8 mL/mol (P(6)). A model is developed that explains the dependence of DeltaV(o)(LM) on the kinetic state by the electrostriction effect of charges, which are formed and neutralized during the L/M transition. PMID:12496115

Stabilization of different types of transition states in a single enzyme active site: QM/MM analysis of enzymes in the alkaline phosphatase superfamily.

PubMed

Hou, Guanhua; Cui, Qiang

2013-07-17

The first step for the hydrolysis of a phosphate monoester (pNPP(2-)) in enzymes of the alkaline phosphatase (AP) superfamily, R166S AP and wild-type NPP, is studied using QM/MM simulations based on an approximate density functional theory (SCC-DFTBPR) and a recently introduced QM/MM interaction Hamiltonian. The calculations suggest that similar loose transition states are involved in both enzymes, despite the fact that phosphate monoesters are the cognate substrates for AP but promiscuous substrates for NPP. The computed loose transition states are clearly different from the more synchronous ones previously calculated for diester reactions in the same AP enzymes. Therefore, our results explicitly support the proposal that AP enzymes are able to recognize and stabilize different types of transition states in a single active site. Analysis of the structural features of computed transition states indicates that the plastic nature of the bimetallic site plays a minor role in accommodating multiple types of transition states and that the high degree of solvent accessibility of the AP active site also contributes to its ability to stabilize diverse transition-state structures without the need of causing large structural distortions of the bimetallic motif. The binding mode of the leaving group in the transition state highlights that vanadate may not always be an ideal transition state analog for loose phosphoryl transfer transition states.

Possible reason for the unusual regioselectivity in nucleophilic ring opening of trisubstituted aziridines under mildly basic conditions.

PubMed

Kelley, Brandon T; Carroll, Patrick; Joullié, Madeleine M

2014-06-06

2,2,3-Trisubstituted aziridines are known to undergo ring opening at the more substituted carbon under mildly basic conditions. However, the reason for the formation of the more sterically encumbered product has never been examined. Several trisubstituted aziridines, with different substitution patterns at the C-2 and C-3 carbons, were synthesized to change the electronics of the aziridine ring system. These changes had no effect on the regioselectivity of the ring-opening reaction. Using the B3LYP/6-31G* DFT basis set it was determined that the transition state for opening at the more substituted carbon proceeds at a lower energy than the transition state at the less substituted carbon.

The protonation of N2O reexamined - A case study on the reliability of various electron correlation methods for minima and transition states

NASA Technical Reports Server (NTRS)

Martin, J. M. L.; Lee, Timothy J.

1993-01-01

The protonation of N2O and the intramolecular proton transfer in N2OH(+) are studied using various basis sets and a variety of methods, including second-order many-body perturbation theory (MP2), singles and doubles coupled cluster (CCSD), the augmented coupled cluster (CCSD/T/), and complete active space self-consistent field (CASSCF) methods. For geometries, MP2 leads to serious errors even for HNNO(+); for the transition state, only CCSD/T/ produces a reliable geometry due to serious nondynamical correlation effects. The proton affinity at 298.15 K is estimated at 137.6 kcal/mol, in close agreement with recent experimental determinations of 137.3 +/- 1 kcal/mol.

ExoMol molecular line lists - XXVI: spectra of SH and NS

NASA Astrophysics Data System (ADS)

Yurchenko, Sergei N.; Bond, Wesley; Gorman, Maire N.; Lodi, Lorenzo; McKemmish, Laura K.; Nunn, William; Shah, Rohan; Tennyson, Jonathan

2018-04-01

Line lists for the sulphur-containing molecules SH (the mercapto radical) and NS are computed as part of the ExoMol project. These line lists consider transitions within the X 2Π ground state for 32SH, 33SH, 34SH and 32SD, and 14N32S, 14N33S, 14N34S, 14N36S and 15N32S. Ab initio potential energy (PEC) and spin-orbit coupling (SOC) curves are computed and then improved by fitting to experimentally observed transitions. Fully ab initio dipole moment curves (DMCs) computed at high level of theory are used to produce the final line lists. For SH, our fit gives a root-mean-square (rms) error of 0.03 cm-1 between the observed (vmax = 4, Jmax = 34.5) and calculated transitions wavenumbers; this is extrapolated such that all X 2Π rotational-vibrational-electronic (rovibronic) bound states are considered. For 32SH the resulting line list contains about 81 000 transitions and 2 300 rovibronic states, considering levels up to vmax = 14 and Jmax = 60.5. For NS the refinement used a combination of experimentally determined frequencies and energy levels and led to an rms fitting error of 0.002 cm-1. Each NS calculated line list includes around 2.8 million transitions and 31 000 rovibronic states with a vibrational range up to v = 53 and rotational range to J = 235.5, which covers up to 23 000 cm-1. Both line lists should be complete for temperatures up to 5000 K. Example spectra simulated using this line list are shown and comparisons made to the existing data in the CDMS database. The line lists are available from the CDS (http://cdsarc.u-strasbg.fr) and ExoMol (www.exomol.com) data bases.

Skyrme RPA description of γ-vibrational states in rare-earth nuclei

NASA Astrophysics Data System (ADS)

Nesterenko, V. O.; Kartavenko, V. G.; Kleinig, W.; Kvasil, J.; Repko, A.; Jolos, R. V.; Reinhard, P.-G.

2016-01-01

The lowest γ-vibrational states with Kπ = 2+γ in well-deformed Dy, Er and Yb isotopes are investigated within the self-consistent separable quasiparticle random-phase-approximation (QRPA) approach based on the Skyrme functional. The energies Eγ and reduced transition probabilities B(E2)γ of the states are calculated with the Skyrme force SV-mas10. We demonstrate the strong effect of the pairing blocking on the energies of γ-vibrational states. It is also shown that collectivity of γ-vibrational states is strictly determined by keeping the Nilsson selection rules in the corresponding lowest 2qp configurations.

Spin-dependent evolution of collectivity in 112Te

NASA Astrophysics Data System (ADS)

Doncel, M.; Bäck, T.; Qi, C.; Cullen, D. M.; Hodge, D.; Cederwall, B.; Taylor, M. J.; Procter, M.; Giles, M.; Auranen, K.; Grahn, T.; Greenlees, P. T.; Jakobsson, U.; Julin, R.; Juutinen, S.; HerzáÅ, A.; Konki, J.; Pakarinen, J.; Partanen, J.; Peura, P.; Rahkila, P.; Ruotsalainen, P.; Sandzelius, M.; Sarén, J.; Scholey, C.; Sorri, J.; Stolze, S.; Uusitalo, J.

2017-11-01

The evolution of collectivity with spin along the yrast line in the neutron-deficient nucleus 112Te has been studied by measuring the reduced transition probability of excited states in the yrast band. In particular, the lifetimes of the 4+ and 6+ excited states have been determined by using the recoil distance Doppler-shift method. The results are discussed using both large-scale shell-model and total Routhian surface calculations.

Lifetime measurement of high spin states in (75) Kr

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheikh, Javid; Trivedi, T.; Maurya, K.

2010-01-01

The lifetimes of high spin states of {sup 75}Kr have been determined via {sup 50}Cr ({sup 28}Si, 2pn) {sup 75}Kr reaction in positive parity band using the Doppler-shift attenuation method. The transition quadrupole moments Q deduced from lifetime measurements have been compared with {sup 75}Br. Experimental results obtained from lifetime measurement are interpreted in the framework of projected shell model.

The Effect of Recreational Activities on the Elimination of State-Trait Anxiety of the Students Who Will Take the SBS Placement Test

ERIC Educational Resources Information Center

Birtürk, Atilay; Karagün, Elif

2015-01-01

The purpose of this study is to examine whether recreational activities have an effect on the elimination of state-trait anxiety of the students who will take the "SBS Placement Test" which is an exam for transition from secondary school to high school. For this purpose, as well as an information survey which determined the…

The nuclear magnetic moment of 208Bi and its relevance for a test of bound-state strong-field QED

NASA Astrophysics Data System (ADS)

Schmidt, S.; Billowes, J.; Bissell, M. L.; Blaum, K.; Garcia Ruiz, R. F.; Heylen, H.; Malbrunot-Ettenauer, S.; Neyens, G.; Nörtershäuser, W.; Plunien, G.; Sailer, S.; Shabaev, V. M.; Skripnikov, L. V.; Tupitsyn, I. I.; Volotka, A. V.; Yang, X. F.

2018-04-01

The hyperfine structure splitting in the 6p3 3/2 4S → 6p2 7 s 1/2 4P transition at 307 nm in atomic 208Bi was measured with collinear laser spectroscopy at ISOLDE, CERN. The hyperfine A and B factors of both states were determined with an order of magnitude improved accuracy. Based on these measurements, theoretical input for the hyperfine structure anomaly, and results from hyperfine measurements on hydrogen-like and lithium-like 209Bi80+,82+, the nuclear magnetic moment of 208Bi has been determined to μ (208Bi) = + 4.570 (10)μN. Using this value, the transition energy of the ground-state hyperfine splitting in hydrogen-like and lithium-like 208Bi80+,82+ and their specific difference of -67.491(5)(148) meV are predicted. This provides a means for an experimental confirmation of the cancellation of nuclear structure effects in the specific difference in order to exclude such contributions as the cause of the hyperfine puzzle, the recently reported 7-σ discrepancy between experiment and bound-state strong-field QED calculations of the specific difference in the hyperfine structure splitting of 209Bi80+,82+.

Effects of prophylactic incisional gastropexy on markers of gastric motility in dogs as determined by use of a novel wireless motility device.

PubMed

Gazzola, Krista M; Nelson, Laura L; Fritz, Michele C; Clancy, Michelle R; Hauptman, Joe G

2017-01-01

OBJECTIVE To evaluate effects of laparoscopic-assisted incisional gastropexy (LAIG) on gastric motility in dogs by use of a wireless motility device (WMD). ANIMALS 10 healthy client-owned large or giant-breed dogs. PROCEDURES 10 dogs owned by clients interested in prophylactic LAIG were enrolled. To determine effects of LAIG on gastrointestinal motility in dogs during the nonfed state, each dog was evaluated by use of a noninvasive WMD before and > 4 weeks after LAIG. All dogs underwent LAIG, with or without concurrent elective gonadectomy. Data obtained before and after LAIG were analyzed by use of proprietary software to determine the gastric emptying time, small bowel transit time, large bowel transit time, whole bowel transit time, and motility index. RESULTS No changes in variables were detected between measurements obtained before and after prophylactic LAIG. CONCLUSIONS AND CLINICAL RELEVANCE In this study, prophylactic LAIG did not have an effect on gastrointestinal motility. The WMD was tolerated well by all dogs and appeared to be a safe and effective method for evaluating gastrointestinal motility in this population of dogs.

Nature of phase transitions in Axelrod-like coupled Potts models in two dimensions

NASA Astrophysics Data System (ADS)

Gandica, Yerali; Chiacchiera, Silvia

2016-03-01

We study F coupled q -state Potts models in a two-dimensional square lattice. The interaction between the different layers is attractive to favor a simultaneous alignment in all of them, and its strength is fixed. The nature of the phase transition for zero field is numerically determined for F =2 ,3 . Using the Lee-Kosterlitz method, we find that it is continuous for F =2 and q =2 , whereas it is abrupt for higher values of q and/or F . When a continuous or a weakly first-order phase transition takes place, we also analyze the properties of the geometrical clusters. This allows us to determine the fractal dimension D of the incipient infinite cluster and to examine the finite-size scaling of the cluster number density via data collapse. A mean-field approximation of the model, from which some general trends can be determined, is presented too. Finally, since this lattice model has been recently considered as a thermodynamic counterpart of the Axelrod model of social dynamics, we discuss our results in connection with this one.

Nature of phase transitions in Axelrod-like coupled Potts models in two dimensions.

PubMed

Gandica, Yerali; Chiacchiera, Silvia

2016-03-01

We study F coupled q-state Potts models in a two-dimensional square lattice. The interaction between the different layers is attractive to favor a simultaneous alignment in all of them, and its strength is fixed. The nature of the phase transition for zero field is numerically determined for F = 2,3. Using the Lee-Kosterlitz method, we find that it is continuous for F = 2 and q = 2, whereas it is abrupt for higher values of q and/or F. When a continuous or a weakly first-order phase transition takes place, we also analyze the properties of the geometrical clusters. This allows us to determine the fractal dimension D of the incipient infinite cluster and to examine the finite-size scaling of the cluster number density via data collapse. A mean-field approximation of the model, from which some general trends can be determined, is presented too. Finally, since this lattice model has been recently considered as a thermodynamic counterpart of the Axelrod model of social dynamics, we discuss our results in connection with this one.

Millimeter-wave spectroscopy of CoNO Produced by UV laser photolysis of Co(CO){sub 3}NO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakamoto, Ai; Hayashi, Masato; Harada, Kensuke

2008-10-07

The rotational spectrum of cobalt mononitrosyl (CoNO) produced by ultraviolet photolysis of Co(CO){sub 3}NO was observed in the millimeter-wave region. Seven rotational transitions in the ground state ranging from J=6-5 to 12-11, with hyperfine splittings due to the Co nucleus (I=7/2), were detected in a supersonic jet environment, while higher-frequency transitions in the range from J=29-28 to 35-34 were measured in the ground, {nu}{sub 1}, {nu}{sub 2}, {nu}{sub 3}, and 2{nu}{sub 2} vibrational states using a free-space absorption cell. It was confirmed from the observed spectral pattern that the CoNO molecule has a linear structure with the electronic ground statemore » of {sup 1}{sigma}{sup +} symmetry. The rotational lines in the 2{nu}{sub 2}({sigma}) and {nu}{sub 3} states were observed to be perturbed by Fermi resonance. The equilibrium rotational constant B{sub e} is determined to be 4682.207(15) MHz. The CoN bond length is derived to be 1.5842 A assuming the NO bond length of 1.1823 A. A large nuclear spin-rotation interaction constant, C{sub I}=123.8(11) kHz, was determined, suggesting a {sup 1}{pi} electronic excited state lying close to the ground state.« less

The applications of satellites to communications, navigation and surveillance for aircraft operating over the contiguous United States

NASA Technical Reports Server (NTRS)

Craigie, J. H.; Otten, D. D.; Garabedian, A.; Morrison, D. D.; MALLINCKRODT; ZIPPER

1970-01-01

The objective was to determine on a priority basis the satellite applications to communications, navigation, and surveillance requirements for aircraft operating beyond 1975 over the contiguous United States and adjacent oceanic transition regions, and to determine if and how satellite technology can meet these requirements in a reliable, efficient, and economical manner. Major results and conclusions are as follows: (1) The satellite applications of greatest importance are surveillance and rapid collision warning communications; and (2) The necessary technology is available as demonstrated by an attractive system concept.

Critical behavior of dissipative two-dimensional spin lattices

NASA Astrophysics Data System (ADS)

Rota, R.; Storme, F.; Bartolo, N.; Fazio, R.; Ciuti, C.

2017-04-01

We explore critical properties of two-dimensional lattices of spins interacting via an anisotropic Heisenberg Hamiltonian that are subject to incoherent spin flips. We determine the steady-state solution of the master equation for the density matrix via the corner-space renormalization method. We investigate the finite-size scaling and critical exponent of the magnetic linear susceptibility associated with a dissipative ferromagnetic transition. We show that the von Neumann entropy increases across the critical point, revealing a strongly mixed character of the ferromagnetic phase. Entanglement is witnessed by the quantum Fisher information, which exhibits a critical behavior at the transition point, showing that quantum correlations play a crucial role in the transition.

VUV Fourier-Transform absorption study of the npπ1 Πu-, v, N ←X1 Σg+, v″ = 0,N″ transitions in D2

NASA Astrophysics Data System (ADS)

Glass-Maujean, M.; Jungen, Ch.; Dickenson, G. D.; Ubachs, W.; de Oliveira, N.; Joyeux, D.; Nahon, L.

2015-09-01

The DESIRS beamline of the SOLEIL synchrotron facility, equipped with a vacuum ultraviolet Fourier-Transform spectrometer has been used to measure Q (N″) (N -N″ = 0) absorption transitions of the D2 molecule. Some 212 Q-lines were assigned and their transition frequencies determined up to excitation energies of 137 000 cm-1 above the ground state, thereby extending the earlier work by various authors, and considerably improving the spectral accuracy (<0.1 cm-1). The assignments have been aided by first principles multichannel quantum defect theory (MQDT) calculations which also provide predictions of the autoionization widths of the upper levels.

Insight into the structure of photosynthetic LH2 aggregate from spectroscopy simulations.

PubMed

Rancova, Olga; Sulskus, Juozas; Abramavicius, Darius

2012-07-12

Using the electrostatic model of intermolecular interactions, we obtain the Frenkel exciton Hamiltonian parameters for the chlorophyll Qy band of a photosynthetic peripheral light harvesting complex LH2 of a purple bacteria Rhodopseudomonas acidophila from structural data. The intermolecular couplings are mostly determined by the chlorophyll relative positions, whereas the molecular transition energies are determined by the background charge distribution of the whole complex. The protonation pattern of titratable residues is used as a tunable parameter. By studying several protonation state scenarios for distinct protein groups and comparing the simulated absorption and circular dichroism spectra to experiment, we determine the most probable configuration of the protonation states of various side groups of the protein.

Transit Precovery: Determining Ephemerides for Long-Period TESS Detections with KELT Photometry

NASA Astrophysics Data System (ADS)

Yao, Xinyu; Pepper, Joshua; KELT Collaboration

2018-01-01

The majority of the known exoplanets were discovered by using the transit method such as with Kepler and the upcoming TESS mission. Unlike the Kepler mission which observed stars for several years, 74% of the area to be observed by TESS will only have an observational baseline of 27 days. For those planets with periods longer than 13 days, TESS can only capture one or two transits which means the true ephemerides are difficult to determine. Since the ground based all sky survey project KELT has much longer observation baseline (up to ten years) and monitors fields that overlap with TESS fields, by using KELT photometric data the ephemerides of the single and double-transit events that will be detected by TESS can be determined precisely. By conducting a simulation process to insert transits into KELT light curves and recover periods, we find that KELT photometry can be used to confirm ephemerides with high accuracy for planets of Neptune size or larger with orbital periods as long as a year, and therefore across a wide range of planet equilibrium temperatures. The resulting periods of the signals can then be used by follow-up teams, whether part of the TESS mission or the community-organized TFOP project, to plan and coordinate follow-up observations to confirm these cases as planets, eclipsing binaries, or other false positives, as well as conduct detailed transit observations with facilities like JWST or HST.This project makes use of data from the KELT survey, including support from The Ohio State University, Vanderbilt University, and Lehigh University.

Metabolite profiling and associated gene expression reveal two metabolic shifts during the seed-to-seedling transition in Arabidopsis thaliana.

PubMed

Silva, Anderson Tadeu; Ligterink, Wilco; Hilhorst, Henk W M

2017-11-01

Metabolic and transcriptomic correlation analysis identified two distinctive profiles involved in the metabolic preparation for seed germination and seedling establishment, respectively. Transcripts were identified that may control metabolic fluxes. The transition from a quiescent metabolic state (dry seed) to the active state of a vigorous seedling is crucial in the plant's life cycle. We analysed this complex physiological trait by measuring the changes in primary metabolism that occur during the transition in order to determine which metabolic networks are operational. The transition involves several developmental stages from seed germination to seedling establishment, i.e. between imbibition of the mature dry seed and opening of the cotyledons, the final stage of seedling establishment. We hypothesized that the advancement of growth is associated with certain signature metabolite profiles. Metabolite-metabolite correlation analysis underlined two specific profiles which appear to be involved in the metabolic preparation for seed germination and efficient seedling establishment, respectively. Metabolite profiles were also compared to transcript profiles and although transcriptional changes did not always equate to a proportional metabolic response, in depth correlation analysis identified several transcripts that may directly influence the flux through metabolic pathways during the seed-to-seedling transition. This correlation analysis also pinpointed metabolic pathways which are significant for the seed-to-seedling transition, and metabolite contents that appeared to be controlled directly by transcript abundance. This global view of the transcriptional and metabolic changes during the seed-to-seedling transition in Arabidopsis opens up new perspectives for understanding the complex regulatory mechanism underlying this transition.

Structural changes and fluctuations of proteins. I. A statistical thermodynamic model.

PubMed

Ikegami, A

1977-01-01

A general theory of the structural changes and fluctuations of proteins has been proposed based on statistical thermodynamic considerations at the chain level. The "structure" of protein was assumed to be characterized by the state of secondary bonds between unique pairs of specific sites on peptide chains. Every secondary bond changes between the bonded and unbonded states by thermal agitation and the "structure" is continuously fluctuating. The free energy of the "structural state" that is defined by the fraction of secondary bonds in the bonded state has been expressed by the bond energy, the cooperative interaction between bonds, the mixing entropy of bonds, and the entropy of polypeptide chains. The most probable "structural state" can be simply determined by graphical analysis and the effect of temperature or solvent composition on it is discussed. The temperature dependence of the free energy, the probability distribution of structural states and the specific heat have been calculted for two examples of structural change. The theory predicts two different types of structural changes from the ordered to disorderd state, a "structured transition" and a "gradual structural change" with rising temperature. In the "structural transition", the probability distribution has two maxima in the temperature range of transition. In the "gradual structural change", the probabilty distribution has only one maximum during the change. A considerable fraction of secondary bonds is in the unbounded state and is always fluctuating even in the ordered state at room temperature. Such structural flucutations in a single protein molecule have been discussed quantitatively. The theory is extended to include small molecules which bind to the protein molecule and affect the structural state. The changes of structural state caused by specific and non-specific binding and allosteric effects are explained in a unified manner.

Abnormal Elasticity of Single-Crystal Magnesiosiderite across the Spin Transition in Earth's Lower Mantle

NASA Astrophysics Data System (ADS)

Fu, Suyu; Yang, Jing; Lin, Jung-Fu

2017-01-01

Brillouin light scattering and impulsive stimulated light scattering have been used to determine the full elastic constants of magnesiosiderite [(Mg0.35Fe0.65)CO3 ] up to 70 GPa at room temperature in a diamond-anvil cell. Drastic softening in C11 , C33 , C12 , and C13 elastic moduli associated with the compressive stress component and stiffening in C44 and C14 moduli associated with the shear stress component are observed to occur within the spin transition between ˜42.4 and ˜46.5 GPa . Negative values of C12 and C13 are also observed within the spin transition region. The Born criteria constants for the crystal remain positive within the spin transition, indicating that the mixed-spin state remains mechanically stable. Significant auxeticity can be related to the electronic spin transition-induced elastic anomalies based on the analysis of Poisson's ratio. These elastic anomalies are explained using a thermoelastic model for the rhombohedral system. Finally, we conclude that mixed-spin state ferromagnesite, which is potentially a major deep-carbon carrier, is expected to exhibit abnormal elasticity, including a negative Poisson's ratio of -0.6 and drastically reduced VP by 10%, in Earth's midlower mantle.

Magneto-optical far-infrared absorption spectroscopy of the hole states of indium phosphide

NASA Astrophysics Data System (ADS)

Lewis, R. A.; Wang, Y.-J.

2005-03-01

Far-infrared absorption spectroscopy in magnetic fields of up to 30 T of the zinc acceptor impurity in indium phosphide has revealed for the first time a series of free-hole transitions (Landau-related series) in addition to the familiar bound-hole transitions (Lyman series) as well as hitherto unobserved phonon replicas of both series. Analysis of these data permits the simultaneous direct experimental determination of (i) the hole effective mass, (ii) the species-specific binding energy of the acceptor impurity, (iii) the absolute energy levels of the acceptor excited states of both odd and even parity, (iv) more reliable, and in some cases the only, g factors for acceptor states, through relaxation of the selection rules for phonon replicas, and (v) the LO phonon energy. The method is applicable to other semiconductors and may lead to the reappraisal of their physical parameters.

An equation-of-state-meter of quantum chromodynamics transition from deep learning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pang, Long-Gang; Zhou, Kai; Su, Nan

A primordial state of matter consisting of free quarks and gluons that existed in the early universe a few microseconds after the Big Bang is also expected to form in high-energy heavy-ion collisions. Determining the equation of state (EoS) of such a primordial matter is the ultimate goal of high-energy heavy-ion experiments. Here we use supervised learning with a deep convolutional neural network to identify the EoS employed in the relativistic hydrodynamic simulations of heavy ion collisions. High-level correlations of particle spectra in transverse momentum and azimuthal angle learned by the network act as an effective EoS-meter in deciphering themore » nature of the phase transition in quantum chromodynamics. Finally, such EoS-meter is model-independent and insensitive to other simulation inputs including the initial conditions for hydrodynamic simulations.« less

An equation-of-state-meter of quantum chromodynamics transition from deep learning

DOE PAGES

Pang, Long-Gang; Zhou, Kai; Su, Nan; ...

2018-01-15

A primordial state of matter consisting of free quarks and gluons that existed in the early universe a few microseconds after the Big Bang is also expected to form in high-energy heavy-ion collisions. Determining the equation of state (EoS) of such a primordial matter is the ultimate goal of high-energy heavy-ion experiments. Here we use supervised learning with a deep convolutional neural network to identify the EoS employed in the relativistic hydrodynamic simulations of heavy ion collisions. High-level correlations of particle spectra in transverse momentum and azimuthal angle learned by the network act as an effective EoS-meter in deciphering themore » nature of the phase transition in quantum chromodynamics. Finally, such EoS-meter is model-independent and insensitive to other simulation inputs including the initial conditions for hydrodynamic simulations.« less

Predictor laws for pictorial flight displays

NASA Technical Reports Server (NTRS)

Grunwald, A. J.

1985-01-01

Two predictor laws are formulated and analyzed: (1) a circular path law based on constant accelerations perpendicular to the path and (2) a predictor law based on state transition matrix computations. It is shown that for both methods the predictor provides the essential lead zeros for the path-following task. However, in contrast to the circular path law, the state transition matrix law furnishes the system with additional zeros that entirely cancel out the higher-frequency poles of the vehicle dynamics. On the other hand, the circular path law yields a zero steady-state error in following a curved trajectory with a constant radius. A combined predictor law is suggested that utilizes the advantages of both methods. A simple analysis shows that the optimal prediction time mainly depends on the level of precision required in the path-following task, and guidelines for determining the optimal prediction time are given.

The Pure Rotational Spectrum of KO

NASA Astrophysics Data System (ADS)

Burton, Mark; Russ, Benjamin; Sheridan, Phillip M.; Bucchino, Matthew; Ziurys, Lucy M.

2017-06-01

The pure rotational spectrum of potassium monoxide (KO) has been recorded using millimeter-wave direct absorption spectroscopy. KO was synthesized by the reaction of potassium vapor, produced in a Broida-type oven, with nitrous oxide. No DC discharge was necessary. Eleven rotational transitions belonging to the ^{2}Π_{3/2} spin-orbit component have been measured and have been fit successfully to a case (c) Hamiltonian. Rotational and lambda-doubling constants for this spin-orbit component have been determined. It has been suggested that the ground electronic state of KO is either ^{2}Π (as for LiO and NaO) or ^{2}Σ (as for RbO and CsO), both of which lie close in energy. Recent computational studies favor a ^{2}Σ ground state. Further measurements of the rotational transitions of the ^{2}Π_{1/2} spin-orbit component and the ^{2}Σ state are currently in progress, as well as the potassium hyperfine structure.

Precision measurements on trapped antihydrogen in the ALPHA experiment

NASA Astrophysics Data System (ADS)

Eriksson, S.

2018-03-01

Both the 1S-2S transition and the ground state hyperfine spectrum have been observed in trapped antihydrogen. The former constitutes the first observation of resonant interaction of light with an anti-atom, and the latter is the first detailed measurement of a spectral feature in antihydrogen. Owing to the narrow intrinsic linewidth of the 1S-2S transition and use of two-photon laser excitation, the transition energy can be precisely determined in both hydrogen and antihydrogen, allowing a direct comparison as a test of fundamental symmetry. The result is consistent with CPT invariance at a relative precision of around 2×10-10. This constitutes the most precise measurement of a property of antihydrogen. The hyperfine spectrum of antihydrogen is determined to a relative uncertainty of 4×10-4. The excited state and the hyperfine spectroscopy techniques currently both show sensitivity at the few 100 kHz level on the absolute scale. Here, the most recent work of the ALPHA collaboration on precision spectroscopy of antihydrogen is presented together with an outlook on improving the precision of measurements involving lasers and microwave radiation. Prospects of measuring the Lamb shift and determining the antiproton charge radius in trapped antihydrogen in the ALPHA apparatus are presented. Future perspectives of precision measurements of trapped antihydrogen in the ALPHA apparatus when the ELENA facility becomes available to experiments at CERN are discussed. This article is part of the Theo Murphy meeting issue `Antiproton physics in the ELENA era'.

The Lamb-shift experiment in Muonic helium

NASA Astrophysics Data System (ADS)

Nebel, T.; Amaro, F. D.; Antognini, A.; Biraben, F.; Cardoso, J. M. R.; Covita, D. S.; Dax, A.; Fernandes, L. M. P.; Gouvea, A. L.; Graf, T.; Hänsch, T. W.; Hildebrandt, M.; Indelicato, P.; Julien, L.; Kirch, K.; Kottmann, F.; Liu, Y.-W.; Monteiro, C. M. B.; Nez, F.; Santos, J. M. F. dos; Schuhmann, K.; Taqqu, D.; Veloso, J. F. C. A.; Voss, A.; Pohl, R.

2012-12-01

We propose to measure several transition frequencies between the 2 S and the 2 P states (Lamb shift) in muonic helium ions ( μ 4He + and μ 3He + ) by means of laser spectroscopy, in order to determine the alpha-particle and helion root-mean-square (rms) charge radius. In addition, the fine and hyperfine structure components will be revealed, and the magnetic moment distribution radius will be determined. The contribution of the finite size effect to the Lamb shift (2 S - 2 P energy difference) in μHe + is as high as 20 %. Therefore a measurement of the transition frequencies with a moderate (for laser spectroscopy) precision of 50 ppm (corresponding to 1/20 of the linewidth) will lead to a determination of the nuclear rms charge radii with a relative accuracy of 3 ×10 - 4 (equivalent to 0.0005 fm). The limiting factor for the extraction of the radii from the Lamb shift measurements is given by the uncertainty of the nuclear polarizability contribution. Combined with an ongoing experiment at MPQ aiming to measure the 1 S - 2 S transition frequency in the helium ion, the Lamb shift measurement in μHe + will lead to a sensitive test of problematic and challenging bound-state QED terms. This measurement will also help to clarify the discrepancy found in our previous μ p experiment. Additionally, a precise knowledge of the absolute nuclear radii of the He isotopes and the hyperfine splitting of μ 3He + provide a relevant test of few-nucleon theories.

The Lamb-shift experiment in Muonic helium

NASA Astrophysics Data System (ADS)

Nebel, T.; Amaro, F. D.; Antognini, A.; Biraben, F.; Cardoso, J. M. R.; Covita, D. S.; Dax, A.; Fernandes, L. M. P.; Gouvea, A. L.; Graf, T.; Hänsch, T. W.; Hildebrandt, M.; Indelicato, P.; Julien, L.; Kirch, K.; Kottmann, F.; Liu, Y.-W.; Monteiro, C. M. B.; Nez, F.; Santos, J. M. F. dos; Schuhmann, K.; Taqqu, D.; Veloso, J. F. C. A.; Voss, A.; Pohl, R.

We propose to measure several transition frequencies between the 2S and the 2P states (Lamb shift) in muonic helium ions (μ 4He + and μ 3He + ) by means of laser spectroscopy, in order to determine the alpha-particle and helion root-mean-square (rms) charge radius. In addition, the fine and hyperfine structure components will be revealed, and the magnetic moment distribution radius will be determined. The contribution of the finite size effect to the Lamb shift (2S - 2P energy difference) in μHe + is as high as 20 %. Therefore a measurement of the transition frequencies with a moderate (for laser spectroscopy) precision of 50 ppm (corresponding to 1/20 of the linewidth) will lead to a determination of the nuclear rms charge radii with a relative accuracy of 3 ×10 - 4 (equivalent to 0.0005 fm). The limiting factor for the extraction of the radii from the Lamb shift measurements is given by the uncertainty of the nuclear polarizability contribution. Combined with an ongoing experiment at MPQ aiming to measure the 1S - 2S transition frequency in the helium ion, the Lamb shift measurement in μHe + will lead to a sensitive test of problematic and challenging bound-state QED terms. This measurement will also help to clarify the discrepancy found in our previous μ p experiment. Additionally, a precise knowledge of the absolute nuclear radii of the He isotopes and the hyperfine splitting of μ 3He + provide a relevant test of few-nucleon theories.

Optimizing model: insemination, replacement, seasonal production, and cash flow.

PubMed

DeLorenzo, M A; Spreen, T H; Bryan, G R; Beede, D K; Van Arendonk, J A

1992-03-01

Dynamic programming to solve the Markov decision process problem of optimal insemination and replacement decisions was adapted to address large dairy herd management decision problems in the US. Expected net present values of cow states (151,200) were used to determine the optimal policy. States were specified by class of parity (n = 12), production level (n = 15), month of calving (n = 12), month of lactation (n = 16), and days open (n = 7). Methodology optimized decisions based on net present value of an individual cow and all replacements over a 20-yr decision horizon. Length of decision horizon was chosen to ensure that optimal policies were determined for an infinite planning horizon. Optimization took 286 s of central processing unit time. The final probability transition matrix was determined, in part, by the optimal policy. It was estimated iteratively to determine post-optimization steady state herd structure, milk production, replacement, feed inputs and costs, and resulting cash flow on a calendar month and annual basis if optimal policies were implemented. Implementation of the model included seasonal effects on lactation curve shapes, estrus detection rates, pregnancy rates, milk prices, replacement costs, cull prices, and genetic progress. Other inputs included calf values, values of dietary TDN and CP per kilogram, and discount rate. Stochastic elements included conception (and, thus, subsequent freshening), cow milk production level within herd, and survival. Validation of optimized solutions was by separate simulation model, which implemented policies on a simulated herd and also described herd dynamics during transition to optimized structure.

Quantitative theoretical analysis of lifetimes and decay rates relevant in laser cooling BaH

NASA Astrophysics Data System (ADS)

Moore, Keith; Lane, Ian C.

2018-05-01

Tiny radiative losses below the 0.1% level can prove ruinous to the effective laser cooling of a molecule. In this paper the laser cooling of a hydride is studied with rovibronic detail using ab initio quantum chemistry in order to document the decays to all possible electronic states (not just the vibrational branching within a single electronic transition) and to identify the most populated final quantum states. The effect of spin-orbit and associated couplings on the properties of the lowest excited states of BaH are analysed in detail. The lifetimes of the A2Π1/2, H2Δ3/2 and E2Π1/2 states are calculated (136 ns, 5.8 μs and 46 ns respectively) for the first time, while the theoretical value for B2 Σ1/2+ is in good agreement with experiments. Using a simple rate model the numbers of absorption-emission cycles possible for both one- and two-colour cooling on the competing electronic transitions are determined, and it is clearly demonstrated that the A2Π - X2Σ+ transition is superior to B2Σ+ - X2Σ+ , where multiple tiny decay channels degrade its efficiency. Further possible improvements to the cooling method are proposed.

Mechanochemical effect in the iron(III) spin crossover complex [Fe(3-MeO-salenEt2]PF6 as studied by heat capacity calorimetry.

PubMed

Sorai, Michio; Burriel, Ramón; Westrum, Edgar F; Hendrickson, David N

2008-04-10

Magnetic and thermal properties of the iron(III) spin crossover complex [Fe(3MeO-salenEt)(2)]PF(6) are very sensitive to mechanochemical perturbations. Heat capacities for unperturbed and differently perturbed samples were precisely determined by adiabatic calorimetry at temperatures in the 10-300 K range. The unperturbed compound shows a cooperative spin crossover transition at 162.31 K, presenting a hysteresis of 2.8 K. The anomalous enthalpy and entropy contents of the transition were evaluated to be Delta(trs)H = 5.94 kJ mol(-1) and Delta(trs)S = 36.7 J K(-1) mol(-1), respectively. By mechanochemical treatments, (1) the phase transition temperature was lowered by 1.14 K, (2) the enthalpy and entropy gains at the phase transition due to the spin crossover phenomenon were diminished to Delta(trs)H = 4.94 kJ mol(-1) and Delta(trs)S = 31.1 J K(-1) mol(-1), and (3) the lattice heat capacities were larger than those of the unperturbed sample over the whole temperature range. In spite of different mechanical perturbations (grinding with a mortar and pestle and grinding in a ball-mill), two sets of heat capacity measurements provided basically the same results. The mechanochemical perturbation exerts its effect more strongly on the low-spin state than on the high-spin state. It shows a substantial increase of the number of iron(III) ions in the high-spin state below the transition temperature. The heat capacities of the diamagnetic cobalt(III) analogue [Co(3MeO-salenEt)(2)]PF(6) also were measured. The lattice heat capacity of the iron compounds has been estimated from either the measurements on the cobalt complex using a corresponding states law or the effective frequency distribution method. These estimations have been used for the evaluation of the transition anomaly.

Automated Transition State Search and Its Application to Diverse Types of Organic Reactions.

PubMed

Jacobson, Leif D; Bochevarov, Art D; Watson, Mark A; Hughes, Thomas F; Rinaldo, David; Ehrlich, Stephan; Steinbrecher, Thomas B; Vaitheeswaran, S; Philipp, Dean M; Halls, Mathew D; Friesner, Richard A

2017-11-14

Transition state search is at the center of multiple types of computational chemical predictions related to mechanistic investigations, reactivity and regioselectivity predictions, and catalyst design. The process of finding transition states in practice is, however, a laborious multistep operation that requires significant user involvement. Here, we report a highly automated workflow designed to locate transition states for a given elementary reaction with minimal setup overhead. The only essential inputs required from the user are the structures of the separated reactants and products. The seamless workflow combining computational technologies from the fields of cheminformatics, molecular mechanics, and quantum chemistry automatically finds the most probable correspondence between the atoms in the reactants and the products, generates a transition state guess, launches a transition state search through a combined approach involving the relaxing string method and the quadratic synchronous transit, and finally validates the transition state via the analysis of the reactive chemical bonds and imaginary vibrational frequencies as well as by the intrinsic reaction coordinate method. Our approach does not target any specific reaction type, nor does it depend on training data; instead, it is meant to be of general applicability for a wide variety of reaction types. The workflow is highly flexible, permitting modifications such as a choice of accuracy, level of theory, basis set, or solvation treatment. Successfully located transition states can be used for setting up transition state guesses in related reactions, saving computational time and increasing the probability of success. The utility and performance of the method are demonstrated in applications to transition state searches in reactions typical for organic chemistry, medicinal chemistry, and homogeneous catalysis research. In particular, applications of our code to Michael additions, hydrogen abstractions, Diels-Alder cycloadditions, carbene insertions, and an enzyme reaction model involving a molybdenum complex are shown and discussed.

Selective ultrafast probing of transient hot chemisorbed and precursor states of CO on Ru(0001).

PubMed

Beye, M; Anniyev, T; Coffee, R; Dell'Angela, M; Föhlisch, A; Gladh, J; Katayama, T; Kaya, S; Krupin, O; Møgelhøj, A; Nilsson, A; Nordlund, D; Nørskov, J K; Öberg, H; Ogasawara, H; Pettersson, L G M; Schlotter, W F; Sellberg, J A; Sorgenfrei, F; Turner, J J; Wolf, M; Wurth, W; Oström, H

2013-05-03

We have studied the femtosecond dynamics following optical laser excitation of CO adsorbed on a Ru surface by monitoring changes in the occupied and unoccupied electronic structure using ultrafast soft x-ray absorption and emission. We recently reported [M. Dell'Angela et al. Science 339, 1302 (2013)] a phonon-mediated transition into a weakly adsorbed precursor state occurring on a time scale of >2 ps prior to desorption. Here we focus on processes within the first picosecond after laser excitation and show that the metal-adsorbate coordination is initially increased due to hot-electron-driven vibrational excitations. This process is faster than, but occurs in parallel with, the transition into the precursor state. With resonant x-ray emission spectroscopy, we probe each of these states selectively and determine the respective transient populations depending on optical laser fluence. Ab initio molecular dynamics simulations of CO adsorbed on Ru(0001) were performed at 1500 and 3000 K providing insight into the desorption process.

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

PubMed

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic cations at their transition states. These compensating effects from electrostatic stabilization depend on how similar the charge density in these organic cations is to that in the proton removed. Cations with more localized charge favor strong electrostatic interactions with anions and form more stable ionic structures than do cations with more diffuse charges. Ion-pairs at elimination transition states contain cations with higher local charge density at the sp(2) carbon than for isomerization transition states; as a result, these ion-pairs recover a larger fraction of the deprotonation energy, and, consequently, their reactions become less sensitive to acid strength. These concepts lead us to conclude that the energetic difficulty of a catalytic reaction, imposed by gas-phase reactant proton affinities in transition state analogues, does not determine its sensitivity to the acid strength of solid catalysts.

Two distinct overstretched DNA structures revealed by single-molecule thermodynamics measurements

PubMed Central

Zhang, Xinghua; Chen, Hu; Fu, Hongxia; Doyle, Patrick S.; Yan, Jie

2012-01-01

Double-stranded DNA is a dynamic molecule whose structure can change depending on conditions. While there is consensus in the literature about many structures DNA can have, the state of highly-stretched DNA is still not clear. Several groups have shown that DNA in the torsion-unconstrained B-form undergoes an “overstretching” transition at a stretching force of around 65 pN, which leads to approximately 1.7-fold elongation of the DNA contour length. Recent experiments have revealed that two distinct structural transitions are involved in the overstretching process: (i) a hysteretic “peeling” off one strand from its complementary strand, and (ii) a nonhysteretic transition that leads to an undetermined DNA structure. We report the first simultaneous determination of the entropy (ΔS) and enthalpy changes (ΔH) pertaining to these respective transitions. For the hysteretic peeling transition, we determined ΔS ∼ 20 cal/(K.mol) and ΔH ∼ 7 kcal/mol. In the case of the nonhysteretic transition, ΔS ∼ -3 cal/(K.mol) and ΔH ∼ 1 kcal/mol. Furthermore, the response of the transition force to salt concentration implies that the two DNA strands are spatially separated after the hysteretic peeling transition. In contrast, the corresponding response after the nonhysteretic transition indicated that the strands remained in close proximity. The selection between the two transitions depends on DNA base-pair stability, and it can be illustrated by a multidimensional phase diagram. Our results provide important insights into the thermodynamics of DNA overstretching and conformational structures of overstretched DNA that may play an important role in vivo. PMID:22532662

Document Ranking Based upon Markov Chains.

ERIC Educational Resources Information Center

Danilowicz, Czeslaw; Balinski, Jaroslaw

2001-01-01

Considers how the order of documents in information retrieval responses are determined and introduces a method that uses a probabilistic model of a document set where documents are regarded as states of a Markov chain and where transition probabilities are directly proportional to similarities between documents. (Author/LRW)

Combined Influence of Landscape Composition and Nutrient Inputs on Lake Trophic Structure

EPA Science Inventory

The concentration of chlorophyll a is a measure of the biological productivity of a lake and is largely (but not exclusively) determined by available nutrients. As nutrient inputs increase, productivity increases and lakes transition from low trophic state (e.g. oligotrophic) to...

Paramagnetic and glass transitions in sudoku

NASA Astrophysics Data System (ADS)

Williams, A.; Ackland, G. J.

2012-09-01

We study the statistical mechanics of a model glassy system based on sudoku, a familiar and popular mathematical puzzle. Sudoku puzzles provide a very rare example of a class of frustrated systems with a unique ground state without symmetry. Here, the puzzle is recast as a thermodynamic system where the number of violated rules defines the energy. We use Monte Carlo simulation to show that the “sudoku Hamiltonian” exhibits two transitions as a function of temperature, a paramagnetic, and a glass transition. Of these, the intermediate condensed phase is the only one that visits the ground state (i.e., it solves the puzzle, though this is not the purpose of the study). Both transitions are associated with an entropy change, paramagnetism measured from the dynamics of the Monte Carlo run, showing a peak in specific heat, while the residual glass entropy is determined by finding multiple instances of the glass by repeated annealing. There are relatively few such simple models for frustrated or glassy systems that exhibit both ordering and glass transitions; sudoku puzzles are unique for the ease with which they can be obtained, with the proof of the existence of a unique ground state via the satisfiability of all constraints. Simulations suggest that in the glass phase there is an increase in information entropy with lowering temperature. In fact, we have shown that sudoku puzzles have the type of rugged energy landscape with multiple minima that typifies glasses in many physical systems. This puzzling result is a manifestation of the paradox of the residual glass entropy. These readily available puzzles can now be used as solvable model Hamiltonian systems for studying the glass transition.

Analytic functions for potential energy curves, dipole moments, and transition dipole moments of LiRb molecule.

PubMed

You, Yang; Yang, Chuan-Lu; Wang, Mei-Shan; Ma, Xiao-Guang; Liu, Wen-Wang; Wang, Li-Zhi

2016-01-15

The analytic potential energy functions (APEFs) of the X(1)Σ(+), 2(1)Σ(+), a(3)Σ(+), and 2(3)Σ(+) states of the LiRb molecule are obtained using Morse long-range potential energy function with damping function and nonlinear least-squares method. These calculations were based on the potential energy curves (PECs) calculated using the multi-reference configuration interaction (MRCI) method. The reliability of the APEFs is confirmed using the curves of their first and second derivatives. By using the obtained APEFs, the rotational and vibrational energy levels of the states are determined by solving the Schrödinger equation of nuclear movement. The spectroscopic parameters, which are deduced using Dunham expansion, and the obtained rotational and vibrational levels are compared with the reported theoretical and experimental values. The correlation effect of the electrons of the inner shell remarkably improves the results compared with the experimental spectroscopic parameters. For the first time, the APEFs for the dipole moments and transition dipole moments of the states have been determined based on the curves obtained from the MRCI calculations. Copyright © 2015 Elsevier B.V. All rights reserved.

Disorder-Induced Topological State Transition in Photonic Metamaterials

NASA Astrophysics Data System (ADS)

Liu, Changxu; Gao, Wenlong; Yang, Biao; Zhang, Shuang

2017-11-01

The topological state transition has been widely studied based on the quantized topological band invariant such as the Chern number for the system without intense randomness that may break the band structures. We numerically demonstrate the disorder-induced state transition in the photonic topological systems for the first time. Instead of applying the ill-defined topological band invariant in a disordered system, we utilize an empirical parameter to unambiguously illustrate the state transition of the topological metamaterials. Before the state transition, we observe a robust surface state with well-confined electromagnetic waves propagating unidirectionally, immune to the disorder from permittivity fluctuation up to 60% of the original value. During the transition, a hybrid state composed of a quasiunidirectional surface mode and intensively localized hot spots is established, a result of the competition between the topological protection and Anderson localization.

First high resolution analysis of the 3ν2 and 3ν2 -ν2 bands of 32S16O2

NASA Astrophysics Data System (ADS)

Ulenikov, O. N.; Bekhtereva, E. S.; Gromova, O. V.; Berezkin, K. B.; Horneman, V.-M.; Sydow, C.; Maul, C.; Bauerecker, S.

2017-11-01

The second bending overtone band 3ν2 of sulfur dioxide has been studied for the first time with high resolution rotation-vibration spectroscopy. The 1530 transitions involving 728 upper state energy levels with Jmax.= 53 and Kamax . = 15 have been assigned to the 3ν2 band. The 746 transitions belonging to the 3ν2 -ν2 "hot" band have been also assigned in the region of 950-1100 cm-1. For the analysis of the assigned transitions, an effective Hamiltonian of an isolated (030) vibrational state (the Watson operator in A-reduction and Ir representation) was used. Set of 9 varied parameters was determined which reproduce the initial experimental data with the drms deviations of 9.0 ×10-4 cm-1 and 9.8 ×10-4 cm-1 for the 3ν2 and 3ν2 -ν2 bands, which are comparable with the experimental uncertainties.

Numerical study of Potts models with aperiodic modulations: influence on first-order transitions

NASA Astrophysics Data System (ADS)

Branco, Nilton; Girardi, Daniel

2012-02-01

We perform a numerical study of Potts models on a rectangular lattice with aperiodic interactions along one spatial direction. The number of states q is such that the transition is a first-order one for the uniform model. The Wolff algorithm is employed, for many lattice sizes, allowing for a finite-size scaling analyses to be carried out. Three different self-dual aperiodic sequences are employed, such that the exact critical temperature is known: this leads to precise results for the exponents. We analyze models with q=6 and 15 and show that the Harris-Luck criterion, originally introduced in the study of continuous transitions, is obeyed also for first-order ones. The new universality class that emerges for relevant aperiodic modulations depends on the number of states of the Potts model, as obtained elsewhere for random disorder, and on the aperiodic sequence. We determine the occurrence of log-periodic behavior, as expected for models with aperiodic modulated interactions.

Molecular Motor-Induced Instabilities and Cross Linkers Determine Biopolymer Organization

PubMed Central

Smith, D.; Ziebert, F.; Humphrey, D.; Duggan, C.; Steinbeck, M.; Zimmermann, W.; Käs, J.

2007-01-01

All eukaryotic cells rely on the active self-organization of protein filaments to form a responsive intracellular cytoskeleton. The necessity of motility and reaction to stimuli additionally requires pathways that quickly and reversibly change cytoskeletal organization. While thermally driven order-disorder transitions are, from the viewpoint of physics, the most obvious method for controlling states of organization, the timescales necessary for effective cellular dynamics would require temperatures exceeding the physiologically viable temperature range. We report a mechanism whereby the molecular motor myosin II can cause near-instantaneous order-disorder transitions in reconstituted cytoskeletal actin solutions. When motor-induced filament sliding diminishes, the actin network structure rapidly and reversibly self-organizes into various assemblies. Addition of stable cross linkers was found to alter the architectures of ordered assemblies. These isothermal transitions between dynamic disorder and self-assembled ordered states illustrate that the interplay between passive crosslinking and molecular motor activity plays a substantial role in dynamic cellular organization. PMID:17604319

Wave vector modification of the infinite order sudden approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachs, J.G.; Bowman, J.M.

1980-10-15

A simple method is proposed to modify the infinite order sudden approximation (IOS) in order to extend its region of quantitative validity. The method involves modifying the phase of the IOS scattering matrix to include a part calculated at the outgoing relative kinetic energy as well as a part calculated at the incoming kinetic energy. An immediate advantage of this modification is that the resulting S matrix is symmetric. We also present a closely related method in which the relative kinetic energies used in the calculation of the phase are determined from quasiclassical trajectory calculations. A set of trajectories ismore » run with the initial state being the incoming state, and another set is run with the initial state being the outgoing state, and the average final relative kinetic energy of each set is obtained. One part of the S-operator phase is then calculated at each of these kinetic energies. We apply these methods to vibrationally inelastic collinear collisions of an atom and a harmonic oscillator, and calculate transition probabilities P/sub n/1..-->..nf for three model systems. For systems which are sudden, or nearly so, the agreement with exact quantum close-coupling calculations is substantially improved over standard IOS ones when ..delta..n=such thatub f/-n/sub i/ is large, and the corresponding transition probability is small, i.e., less than 0.1. However, the modifications we propose will not improve the accuracy of the IOS transition probabilities for any collisional system unless the standard form of IOS already gives at least qualitative agreement with exact quantal calculations. We also suggest comparisons between some classical quantities and sudden predictions which should help in determining the validity of the sudden approximation. This is useful when exact quantal data is not available for comparison.« less

Wave vector modification of the infinite order sudden approximation

NASA Astrophysics Data System (ADS)

Sachs, Judith Grobe; Bowman, Joel M.

1980-10-01

A simple method is proposed to modify the infinite order sudden approximation (IOS) in order to extend its region of quantitative validity. The method involves modifying the phase of the IOS scattering matrix to include a part calculated at the outgoing relative kinetic energy as well as a part calculated at the incoming kinetic energy. An immediate advantage of this modification is that the resulting S matrix is symmetric. We also present a closely related method in which the relative kinetic energies used in the calculation of the phase are determined from quasiclassical trajectory calculations. A set of trajectories is run with the initial state being the incoming state, and another set is run with the initial state being the outgoing state, and the average final relative kinetic energy of each set is obtained. One part of the S-operator phase is then calculated at each of these kinetic energies. We apply these methods to vibrationally inelastic collinear collisions of an atom and a harmonic oscillator, and calculate transition probabilities Pn1→nf for three model systems. For systems which are sudden, or nearly so, the agreement with exact quantum close-coupling calculations is substantially improved over standard IOS ones when Δn=‖nf-ni‖ is large, and the corresponding transition probability is small, i.e., less than 0.1. However, the modifications we propose will not improve the accuracy of the IOS transition probabilities for any collisional system unless the standard form of IOS already gives at least qualitative agreement with exact quantal calculations. We also suggest comparisons between some classical quantities and sudden predictions which should help in determining the validity of the sudden approximation. This is useful when exact quantal data is not available for comparison.