Comparative Evaluation of Energy Measurement Models for Transit Systems

DOT National Transportation Integrated Search

1984-02-01

Recent advances in solid state control technology have led to chopper-controlled propulsion systems in urban rail transit applications. Such systems offer the potential for superior train performance through increased train propulsion efficiency and ...

Synthesis of methods for developing transit vehicle specifications.

DOT National Transportation Integrated Search

2014-06-01

The Michigan Department of Transportation (MDOT) has the objective to thoroughly assess its : transit vehicle specification and procurement program in order to compare best practices from : peer states and identify recommendations for improved effici...

Recognition of human activity characteristics based on state transitions modeling technique

NASA Astrophysics Data System (ADS)

Elangovan, Vinayak; Shirkhodaie, Amir

2012-06-01

Human Activity Discovery & Recognition (HADR) is a complex, diverse and challenging task but yet an active area of ongoing research in the Department of Defense. By detecting, tracking, and characterizing cohesive Human interactional activity patterns, potential threats can be identified which can significantly improve situation awareness, particularly, in Persistent Surveillance Systems (PSS). Understanding the nature of such dynamic activities, inevitably involves interpretation of a collection of spatiotemporally correlated activities with respect to a known context. In this paper, we present a State Transition model for recognizing the characteristics of human activities with a link to a prior contextbased ontology. Modeling the state transitions between successive evidential events determines the activities' temperament. The proposed state transition model poses six categories of state transitions including: Human state transitions of Object handling, Visibility, Entity-entity relation, Human Postures, Human Kinematics and Distance to Target. The proposed state transition model generates semantic annotations describing the human interactional activities via a technique called Casual Event State Inference (CESI). The proposed approach uses a low cost kinect depth camera for indoor and normal optical camera for outdoor monitoring activities. Experimental results are presented here to demonstrate the effectiveness and efficiency of the proposed technique.

An evolutionarily conserved RNase-based mechanism for repression of transcriptional positive autoregulation

PubMed Central

Wurtmann, Elisabeth J.; Ratushny, Alexander V.; Pan, Min; Beer, Karlyn D.; Aitchison, John D.; Baliga, Nitin S.

2014-01-01

Summary It is known that environmental context influences the degree of regulation at the transcriptional and post-transcriptional levels. However, the principles governing the differential usage and interplay of regulation at these two levels are not clear. Here, we show that the integration of transcriptional and post-transcriptional regulatory mechanisms in a characteristic network motif drives efficient environment-dependent state transitions. Through phenotypic screening, systems analysis, and rigorous experimental validation, we discovered an RNase (VNG2099C) in Halobacterium salinarum that is transcriptionally co-regulated with genes of the aerobic physiologic state but acts on transcripts of the anaerobic state. Through modeling and experimentation we show that this arrangement generates an efficient state-transition switch, within which RNase-repression of a transcriptional positive autoregulation (RPAR) loop is critical for shutting down ATP-consuming active potassium uptake to reserve energy required for salinity adaptation under aerobic, high potassium, or dark conditions. Subsequently, we discovered that many Escherichia coli operons with energy-associated functions are also putatively controlled by RPAR indicating that this network motif may have evolved independently in phylogenetically distant organisms. Thus, our data suggest that interplay of transcriptional and post-transcriptional regulation in the RPAR motifis a generalized principle for efficient environment-dependent state transitions across prokaryotes. PMID:24612392

Assessing the efficiency of mass transit systems in the United States.

DOT National Transportation Integrated Search

2017-04-01

Frustrated with increased parking problems, unstable gasoline prices, and stifling traffic congestion, a growing number of : metropolitan city dwellers consider utilizing the mass transit system. Reflecting this sentiment, a ridership of the mass tra...

Efficient Transition Probability Computation for Continuous-Time Branching Processes via Compressed Sensing.

PubMed

Xu, Jason; Minin, Vladimir N

2015-07-01

Branching processes are a class of continuous-time Markov chains (CTMCs) with ubiquitous applications. A general difficulty in statistical inference under partially observed CTMC models arises in computing transition probabilities when the discrete state space is large or uncountable. Classical methods such as matrix exponentiation are infeasible for large or countably infinite state spaces, and sampling-based alternatives are computationally intensive, requiring integration over all possible hidden events. Recent work has successfully applied generating function techniques to computing transition probabilities for linear multi-type branching processes. While these techniques often require significantly fewer computations than matrix exponentiation, they also become prohibitive in applications with large populations. We propose a compressed sensing framework that significantly accelerates the generating function method, decreasing computational cost up to a logarithmic factor by only assuming the probability mass of transitions is sparse. We demonstrate accurate and efficient transition probability computations in branching process models for blood cell formation and evolution of self-replicating transposable elements in bacterial genomes.

Efficient Transition Probability Computation for Continuous-Time Branching Processes via Compressed Sensing

PubMed Central

Xu, Jason; Minin, Vladimir N.

2016-01-01

Branching processes are a class of continuous-time Markov chains (CTMCs) with ubiquitous applications. A general difficulty in statistical inference under partially observed CTMC models arises in computing transition probabilities when the discrete state space is large or uncountable. Classical methods such as matrix exponentiation are infeasible for large or countably infinite state spaces, and sampling-based alternatives are computationally intensive, requiring integration over all possible hidden events. Recent work has successfully applied generating function techniques to computing transition probabilities for linear multi-type branching processes. While these techniques often require significantly fewer computations than matrix exponentiation, they also become prohibitive in applications with large populations. We propose a compressed sensing framework that significantly accelerates the generating function method, decreasing computational cost up to a logarithmic factor by only assuming the probability mass of transitions is sparse. We demonstrate accurate and efficient transition probability computations in branching process models for blood cell formation and evolution of self-replicating transposable elements in bacterial genomes. PMID:26949377

Large impact of reorganization energy on photovoltaic conversion due to interfacial charge-transfer transitions.

PubMed

Fujisawa, Jun-ichi

2015-05-14

Interfacial charge-transfer (ICT) transitions are expected to be a novel charge-separation mechanism for efficient photovoltaic conversion featuring one-step charge separation without energy loss. Photovoltaic conversion due to ICT transitions has been investigated using several TiO2-organic hybrid materials that show organic-to-inorganic ICT transitions in the visible region. In applications of ICT transitions to photovoltaic conversion, there is a significant problem that rapid carrier recombination is caused by organic-inorganic electronic coupling that is necessary for the ICT transitions. In order to solve this problem, in this work, I have theoretically studied light-to-current conversions due to the ICT transitions on the basis of the Marcus theory with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. An apparent correlation between the reported incident photon-to-current conversion efficiencies (IPCE) and calculated reorganization energies was clearly found, in which the IPCE increases with decreasing the reorganization energy consistent with the Marcus theory in the inverted region. This activation-energy dependence was systematically explained by the equation formulated by the Marcus theory based on a simple excited-state kinetic scheme. This result indicates that the reduction of the reorganization energy can suppress the carrier recombination and enhance the IPCE. The reorganization energy is predominantly governed by the structural change in the chemical-adsorption moiety between the ground and ICT excited states. This work provides crucial knowledge for efficient photovoltaic conversion due to ICT transitions.

Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

PubMed

Zhang, Wei; Wang, Zhong-Sheng

2014-07-09

Replacing liquid-state electrolytes with solid-state electrolytes has been proven to be an effective way to improve the durability of dye-sensitized solar cells (DSSCs). We report herein the synthesis of amorphous ionic conductors based on polyhedral oligomeric silsesquioxane (POSS) with low glass transition temperatures for solid-state DSSCs. As the ionic conductor is amorphous and in the elastomeric state at the operating temperature of DSSCs, good pore filling in the TiO2 film and good interfacial contact between the solid-state electrolyte and the TiO2 film can be guaranteed. When the POSS-based ionic conductor containing an allyl group is doped with only iodine as the solid-state electrolyte without any other additives, power conversion efficiency of 6.29% has been achieved with good long-term stability under one-sun soaking for 1000 h.

Free energy landscape of activation in a signaling protein at atomic resolution

PubMed Central

Pontiggia, F.; Pachov, D.V.; Clarkson, M.W.; Villali, J.; Hagan, M.F.; Pande, V.S.; Kern, D.

2015-01-01

The interconversion between inactive and active protein states, traditionally described by two static structures, is at the heart of signaling. However, how folded states interconvert is largely unknown due to the inability to experimentally observe transition pathways. Here we explore the free energy landscape of the bacterial response regulator NtrC by combining computation and NMR, and discover unexpected features underlying efficient signaling. We find that functional states are defined purely in kinetic and not structural terms. The need of a well-defined conformer, crucial to the active state, is absent in the inactive state, which comprises a heterogeneous collection of conformers. The transition between active and inactive states occurs through multiple pathways, facilitated by a number of nonnative transient hydrogen bonds, thus lowering the transition barrier through both entropic and enthalpic contributions. These findings may represent general features for functional conformational transitions within the folded state. PMID:26073309

Intrinsic exciton-state mixing and nonlinear optical properties in transition metal dichalcogenide monolayers

NASA Astrophysics Data System (ADS)

Glazov, M. M.; Golub, L. E.; Wang, G.; Marie, X.; Amand, T.; Urbaszek, B.

2017-01-01

Optical properties of transition metal dichalcogenides monolayers are controlled by Wannier-Mott excitons forming a series of 1 s ,2 s ,2 p ,... hydrogen-like states. We develop the theory of the excited excitonic states energy spectrum fine structure. We predict that p - and s -shell excitons are mixed due to the specific D3 h point symmetry of the transition metal dichalcogenide monolayers. Hence, both s - and p -shell excitons are active in both single- and two-photon processes, providing an efficient mechanism of second harmonic generation. The corresponding contribution to the nonlinear susceptibility is calculated.

Efficiently reducing transition curvature in heat-assisted magnetic recording with state-of-the-art write heads

NASA Astrophysics Data System (ADS)

Vogler, Christoph; Abert, Claas; Bruckner, Florian; Suess, Dieter

2017-05-01

Curvatures of bit transitions on granular media are a serious problem for the read-back process. We address this fundamental issue and propose a possibility to efficiently reduce transition curvatures with state-of-the-art heat-assisted magnetic recording heads. We compare footprints of conventional with those of the proposed head design on different media, consisting of exchange coupled and single phase grains. Additionally, we investigate the impact of various recording parameters, such as the full width at half maximum (FWHM) of the applied heat pulse and the coercivity gradient near the write temperature of the recording grains. The footprints are calculated with a coarse grained model, based on the Landau-Lifshitz-Bloch equation. The presented simulations show a transition curvature reduction of up to 40%, in the case of a medium with exchange coupled grains and a heat pulse with a FWHM of 40 nm. We further give the reason for the straightening of the bit transitions, by means of basic considerations with regard to the effective recording time window of the write process. Besides the transition curvature reduction, the proposed head design yields an improvement of the transition jitter in both down-track and off-track directions.

Object/Shape Recognition Technology: An Assessment of the Feasibility of Implementation at Defense Logistics Agency Disposition Services

DTIC Science & Technology

2015-02-25

provide efficiency and effectively manufacture or inventory items. The industries that benefit from Cognex technology are automotive, food and beverage ...recognition tedmology, Tedmology Readiness Level, PAGES Cost Benefit Analysis, Tedmology Commercialization, Technology Transition 139 16. PRICE CODE 17...Technology Development & Transition Strategy Guidebook xvii UD Ultimate Disposal U.S. United States USAF United States Air Force xviii THIS

Transition of planar Couette flow at infinite Reynolds numbers.

PubMed

Itano, Tomoaki; Akinaga, Takeshi; Generalis, Sotos C; Sugihara-Seki, Masako

2013-11-01

An outline of the state space of planar Couette flow at high Reynolds numbers (Re<10^{5}) is investigated via a variety of efficient numerical techniques. It is verified from nonlinear analysis that the lower branch of the hairpin vortex state (HVS) asymptotically approaches the primary (laminar) state with increasing Re. It is also predicted that the lower branch of the HVS at high Re belongs to the stability boundary that initiates a transition to turbulence, and that one of the unstable manifolds of the lower branch of HVS lies on the boundary. These facts suggest HVS may provide a criterion to estimate a minimum perturbation arising transition to turbulent states at the infinite Re limit.

Λ-enhanced grey molasses on the D2 transition of Rubidium-87 atoms.

PubMed

Rosi, Sara; Burchianti, Alessia; Conclave, Stefano; Naik, Devang S; Roati, Giacomo; Fort, Chiara; Minardi, Francesco

2018-01-22

Laser cooling based on dark states, i.e. states decoupled from light, has proven to be effective to increase the phase-space density of cold trapped atoms. Dark-states cooling requires open atomic transitions, in contrast to the ordinary laser cooling used for example in magneto-optical traps (MOTs), which operate on closed atomic transitions. For alkali atoms, dark-states cooling is therefore commonly operated on the D 1 transition nS 1/2  → nP 1/2 . We show that, for 87 Rb, thanks to the large hyperfine structure separations the use of this transition is not strictly necessary and that "quasi-dark state" cooling is efficient also on the D 2 line, 5S 1/2  → 5P 3/2 . We report temperatures as low as (4.0 ± 0.3) μK and an increase of almost an order of magnitude in the phase space density with respect to ordinary laser sub-Doppler cooling.

Electrostatic transition state stabilization rather than reactant destabilization provides the chemical basis for efficient chorismate mutase catalysis.

PubMed

Burschowsky, Daniel; van Eerde, André; Ökvist, Mats; Kienhöfer, Alexander; Kast, Peter; Hilvert, Donald; Krengel, Ute

2014-12-09

For more than half a century, transition state theory has provided a useful framework for understanding the origins of enzyme catalysis. As proposed by Pauling, enzymes accelerate chemical reactions by binding transition states tighter than substrates, thereby lowering the activation energy compared with that of the corresponding uncatalyzed process. This paradigm has been challenged for chorismate mutase (CM), a well-characterized metabolic enzyme that catalyzes the rearrangement of chorismate to prephenate. Calculations have predicted the decisive factor in CM catalysis to be ground state destabilization rather than transition state stabilization. Using X-ray crystallography, we show, in contrast, that a sluggish variant of Bacillus subtilis CM, in which a cationic active-site arginine was replaced by a neutral citrulline, is a poor catalyst even though it effectively preorganizes chorismate for the reaction. A series of high-resolution molecular snapshots of the reaction coordinate, including the apo enzyme, and complexes with substrate, transition state analog and product, demonstrate that an active site, which is only complementary in shape to a reactive substrate conformer, is insufficient for effective catalysis. Instead, as with other enzymes, electrostatic stabilization of the CM transition state appears to be crucial for achieving high reaction rates.

Generating probabilistic Boolean networks from a prescribed transition probability matrix.

PubMed

Ching, W-K; Chen, X; Tsing, N-K

2009-11-01

Probabilistic Boolean networks (PBNs) have received much attention in modeling genetic regulatory networks. A PBN can be regarded as a Markov chain process and is characterised by a transition probability matrix. In this study, the authors propose efficient algorithms for constructing a PBN when its transition probability matrix is given. The complexities of the algorithms are also analysed. This is an interesting inverse problem in network inference using steady-state data. The problem is important as most microarray data sets are assumed to be obtained from sampling the steady-state.

Transition state-finding strategies for use with the growing string method.

PubMed

Goodrow, Anthony; Bell, Alexis T; Head-Gordon, Martin

2009-06-28

Efficient identification of transition states is important for understanding reaction mechanisms. Most transition state search algorithms require long computational times and a good estimate of the transition state structure in order to converge, particularly for complex reaction systems. The growing string method (GSM) [B. Peters et al., J. Chem. Phys. 120, 7877 (2004)] does not require an initial guess of the transition state; however, the calculation is still computationally intensive due to repeated calls to the quantum mechanics code. Recent modifications to the GSM [A. Goodrow et al., J. Chem. Phys. 129, 174109 (2008)] have reduced the total computational time for converging to a transition state by a factor of 2 to 3. In this work, three transition state-finding strategies have been developed to complement the speedup of the modified-GSM: (1) a hybrid strategy, (2) an energy-weighted strategy, and (3) a substring strategy. The hybrid strategy initiates the string calculation at a low level of theory (HF/STO-3G), which is then refined at a higher level of theory (B3LYP/6-31G(*)). The energy-weighted strategy spaces points along the reaction pathway based on the energy at those points, leading to a higher density of points where the energy is highest and finer resolution of the transition state. The substring strategy is similar to the hybrid strategy, but only a portion of the low-level string is refined using a higher level of theory. These three strategies have been used with the modified-GSM and are compared in three reactions: alanine dipeptide isomerization, H-abstraction in methanol oxidation on VO(x)/SiO(2) catalysts, and C-H bond activation in the oxidative carbonylation of toluene to p-toluic acid on Rh(CO)(2)(TFA)(3) catalysts. In each of these examples, the substring strategy was proved most effective by obtaining a better estimate of the transition state structure and reducing the total computational time by a factor of 2 to 3 compared to the modified-GSM. The applicability of the substring strategy has been extended to three additional examples: cyclopropane rearrangement to propylene, isomerization of methylcyclopropane to four different stereoisomers, and the bimolecular Diels-Alder condensation of 1,3-butadiene and ethylene to cyclohexene. Thus, the substring strategy used in combination with the modified-GSM has been demonstrated to be an efficient transition state-finding strategy for a wide range of types of reactions.

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.

Advanced Vehicle Monitoring And Communication Systems For Bus Transit Benefits And Economic Feasibility

DOT National Transportation Integrated Search

1993-03-01

THIS REPORT ANALYZES THE FEASIBILITY OF ADVANCED VEHICLE MONITORING AND COMMUNICATION (AVM/C) SYSTEMS FOR BUS TRANSIT IN THE UNITED STATES. SUCH SYSTEMS ARE WIDELY USED IN EUROPE AND CANADA TO PROVIDE MORE RELIABLE AND EFFICIENT BUS SERVICES, BUT HAV...

Advanced Vehicle Monitoring And Communication Systems For Bus Transit, Benefits And Economic Feasibility

DOT National Transportation Integrated Search

1991-09-01

THIS REPORT ANALYZES THE FEASIBILITY OF ADVANCED VEHICLE MONITORING AND COMMUNICATION (AVM/C) SYSTEMS FOR BUS TRANSIT IN THE UNITED STATES. SUCH SYSTEMS ARE WIDELY USED IN EUROPE AND CANADA TO PROVIDE MORE RELIABLE AND EFFICIENT BUS SERVICES, BUT HAV...

Highly efficient gel-state dye-sensitized solar cells prepared using propionitrile and poly(vinylidene fluoride-co-hexafluoropropylene)

NASA Astrophysics Data System (ADS)

Venkatesan, Shanmuganathan; Hidayati, Noor; Liu, I.-Ping; Lee, Yuh-Lang

2016-12-01

Propionitrile (PPN) solvent based iodide/triiodide liquid-electrolyte is utilized to prepare highly efficient poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) polymer gel electrolytes (PGEs) of dye-sensitized solar cells, aiming at improving the energy conversion efficiency as well as the stability of gel-state DSSCs. The concentrations effect of the PVdF-HFP on the properties of PGEs and the performance of the corresponding cells are studied. The results show that the in-situ gelation is performed for the PVdF-HFP concentration range of 8-18% at room temperature. However, increasing the concentration of polymer in the PGEs triggers a decrease in the diffusivity and conductivity of the PGEs, but an increase in the phase transition temperature of the PGEs. A high phase transition temperature is obtained for the PGEs with 18 wt% PVdF-HFP, which increase the long-term stability of the gel-state DSSC. By using the 18 wt% PVdF-HFP in the presence of 5 wt% TiO2 nanofillers (NFs), gel-state cells with an efficiency of 8.38% can be obtained, which is higher than that achieved by liquid-state cells (7.55%). After 1000 h test at room temperature (RT) and 50 °C, the cell can retain 96% and 82%, respectively, of its initial efficiency.

Raman-laser spectroscopy of Wannier-Stark states

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

Tackmann, G.; Pelle, B.; Hilico, A.

2011-12-15

Raman lasers are used as a spectroscopic probe of the state of atoms confined in a shallow one-dimensional (1D) vertical lattice. For sufficiently long laser pulses, resolved transitions in the bottom band of the lattice between Wannier Stark states corresponding to neighboring wells are observed. Couplings between such states are measured as a function of the lattice laser intensity and compared to theoretical predictions, from which the lattice depth can be extracted. Limits to the linewidth of these transitions are investigated. Transitions to higher bands can also be induced, as well as between transverse states for tilted Raman beams. Allmore » these features allow for a precise characterization of the trapping potential and for an efficient control of the atomic external degrees of freedom.« less

Photon ratchet intermediate band solar cells

NASA Astrophysics Data System (ADS)

Yoshida, M.; Ekins-Daukes, N. J.; Farrell, D. J.; Phillips, C. C.

2012-06-01

In this paper, we propose an innovative concept for solar power conversion—the "photon ratchet" intermediate band solar cell (IBSC)—which may increase the photovoltaic energy conversion efficiency of IBSCs by increasing the lifetime of charge carriers in the intermediate state. The limiting efficiency calculation for this concept shows that the efficiency can be increased by introducing a fast thermal transition of carriers into a non-emissive state. At 1 sun, the introduction of a "ratchet band" results in an increase of efficiency from 46.8% to 48.5%, due to suppression of entropy generation.

Efficient dynamical correction of the transition state theory rate estimate for a flat energy barrier.

PubMed

Mökkönen, Harri; Ala-Nissila, Tapio; Jónsson, Hannes

2016-09-07

The recrossing correction to the transition state theory estimate of a thermal rate can be difficult to calculate when the energy barrier is flat. This problem arises, for example, in polymer escape if the polymer is long enough to stretch between the initial and final state energy wells while the polymer beads undergo diffusive motion back and forth over the barrier. We present an efficient method for evaluating the correction factor by constructing a sequence of hyperplanes starting at the transition state and calculating the probability that the system advances from one hyperplane to another towards the product. This is analogous to what is done in forward flux sampling except that there the hyperplane sequence starts at the initial state. The method is applied to the escape of polymers with up to 64 beads from a potential well. For high temperature, the results are compared with direct Langevin dynamics simulations as well as forward flux sampling and excellent agreement between the three rate estimates is found. The use of a sequence of hyperplanes in the evaluation of the recrossing correction speeds up the calculation by an order of magnitude as compared with the traditional approach. As the temperature is lowered, the direct Langevin dynamics simulations as well as the forward flux simulations become computationally too demanding, while the harmonic transition state theory estimate corrected for recrossings can be calculated without significant increase in the computational effort.

State-Chart Autocoder

NASA Technical Reports Server (NTRS)

Clark, Kenneth; Watney, Garth; Murray, Alexander; Benowitz, Edward

2007-01-01

A computer program translates Unified Modeling Language (UML) representations of state charts into source code in the C, C++, and Python computing languages. ( State charts signifies graphical descriptions of states and state transitions of a spacecraft or other complex system.) The UML representations constituting the input to this program are generated by using a UML-compliant graphical design program to draw the state charts. The generated source code is consistent with the "quantum programming" approach, which is so named because it involves discrete states and state transitions that have features in common with states and state transitions in quantum mechanics. Quantum programming enables efficient implementation of state charts, suitable for real-time embedded flight software. In addition to source code, the autocoder program generates a graphical-user-interface (GUI) program that, in turn, generates a display of state transitions in response to events triggered by the user. The GUI program is wrapped around, and can be used to exercise the state-chart behavior of, the generated source code. Once the expected state-chart behavior is confirmed, the generated source code can be augmented with a software interface to the rest of the software with which the source code is required to interact.

Computationally efficient characterization of potential energy surfaces based on fingerprint distances

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

Schaefer, Bastian; Goedecker, Stefan, E-mail: stefan.goedecker@unibas.ch

2016-07-21

An analysis of the network defined by the potential energy minima of multi-atomic systems and their connectivity via reaction pathways that go through transition states allows us to understand important characteristics like thermodynamic, dynamic, and structural properties. Unfortunately computing the transition states and reaction pathways in addition to the significant energetically low-lying local minima is a computationally demanding task. We here introduce a computationally efficient method that is based on a combination of the minima hopping global optimization method and the insight that uphill barriers tend to increase with increasing structural distances of the educt and product states. This methodmore » allows us to replace the exact connectivity information and transition state energies with alternative and approximate concepts. Without adding any significant additional cost to the minima hopping global optimization approach, this method allows us to generate an approximate network of the minima, their connectivity, and a rough measure for the energy needed for their interconversion. This can be used to obtain a first qualitative idea on important physical and chemical properties by means of a disconnectivity graph analysis. Besides the physical insight obtained by such an analysis, the gained knowledge can be used to make a decision if it is worthwhile or not to invest computational resources for an exact computation of the transition states and the reaction pathways. Furthermore it is demonstrated that the here presented method can be used for finding physically reasonable interconversion pathways that are promising input pathways for methods like transition path sampling or discrete path sampling.« less

Microwave-optical two-photon excitation of Rydberg states

NASA Astrophysics Data System (ADS)

Tate, D. A.; Gallagher, T. F.

2018-03-01

We report efficient microwave-optical two photon excitation of Rb Rydberg atoms in a magneto-optical trap. This approach allows the excitation of normally inaccessible states and provides a path toward excitation of high-angular-momentum states. The efficiency stems from the elimination of the Doppler width, the use of a narrow-band pulsed laser, and the enormous electric-dipole matrix element connecting the intermediate and final states of the transition. The excitation is efficient in spite of the low optical and microwave powers, of order 1 kW and 1 mW, respectively. This is an application of the large dipole coupling strengths between Rydberg states to achieve two-photon excitation of Rydberg atoms.

Effect of temperature-driven phase transition on energy-storage and -release properties of Pb0.97La0.02[Zr0.55Sn0.30Ti0.15]O3 ceramics

NASA Astrophysics Data System (ADS)

Xu, Ran; Tian, Jingjing; Zhu, Qingshan; Feng, Yujun; Wei, Xiaoyong; Xu, Zhuo

2017-07-01

Temperature-driven phase transition of Pb0.97La0.02[Zr0.55Sn0.30Ti0.15]O3 ceramics was studied, and the consecutive ferroelectric-antiferroelectric-paraelectric (FE-AFE-PE) switching was confirmed. The materials have better dielectric tunability (-82% to 50%) in the AFE state than in the FE state. Also, the phase transition influences the energy-storage and -release performance significantly. A sharp increase in releasable energy density and efficiency was observed due to the temperature-driven FE-AFE transition. Highest releasable energy density, current density, and peak power density were achieved at 130 °C, which was attributed to the highest backward transition field. The stored charge was released completely in AFE and PE states in the microseconds scale, while only a small part of it was released in the FE state. The above results indicate the huge impact of temperature-driven phase transition on dielectrics' performance, which is significant when developing AFE materials working in a wide temperature range.

Photofunctional triplet excited states of cyclometalated Ir(III) complexes: beyond electroluminescence.

PubMed

You, Youngmin; Nam, Wonwoo

2012-11-07

The development of cyclometalated Ir(III) complexes has enabled important breakthroughs in electroluminescence because such complexes permit the efficient population of triplet excited states that give rise to luminescent transitions. The triplet states of Ir(III) complexes are advantageous over those of other transition metal complexes in that their electronic transitions and charge-transfer characteristics are tunable over wide ranges. These favorable properties suggest that Ir(III) complexes have significant potential in a variety of photofunctions other than electroluminescence. In this critical review, we describe recent photonic applications of novel Ir(III) complexes. Ir(III) complexes have been shown to affect the exciton statistics in the active layers of organic photovoltaic cells, thereby improving the photon-to-current conversion efficiencies. Nonlinear optical applications that take advantage of the strong charge-transfer properties of triplet transitions are also discussed. The tunability of the electrochemical potentials facilitates the development of efficient photocatalysis in the context of water photolysis or organic syntheses. The photoredox reactivities of Ir(III) complexes have been employed in studies of charge migration along DNA chains. The photoinduced cytotoxicity of Ir(III) complexes on live cells suggests that the complexes may be useful in photodynamic therapy. Potential biological applications of the complexes include phosphorescence labeling and sensing. Intriguing platforms based on cyclometalated Ir(III) complexes potentially provide novel protein tagging and ratiometric detection. We envision that future research into the photofunctionality of Ir(III) complexes will provide important breakthroughs in a variety of photonic applications.

Reusable fast opening switch

DOEpatents

Van Devender, J.P.; Emin, D.

1983-12-21

A reusable fast opening switch for transferring energy, in the form of a high power pulse, from an electromagnetic storage device such as an inductor into a load. The switch is efficient, compact, fast and reusable. The switch comprises a ferromagnetic semiconductor which undergoes a fast transition between conductive and metallic states at a critical temperature and which undergoes the transition without a phase change in its crystal structure. A semiconductor such as europium rich europhous oxide, which undergoes a conductor to insulator transition when it is joule heated from its conductor state, can be used to form the switch.

Reusable fast opening switch

DOEpatents

Van Devender, John P.; Emin, David

1986-01-01

A reusable fast opening switch for transferring energy, in the form of a high power pulse, from an electromagnetic storage device such as an inductor into a load. The switch is efficient, compact, fast and reusable. The switch comprises a ferromagnetic semiconductor which undergoes a fast transition between conductive and insulating states at a critical temperature and which undergoes the transition without a phase change in its crystal structure. A semiconductor such as europium rich europhous oxide, which undergoes a conductor to insulator transition when it is joule heated from its conductor state, can be used to form the switch.

Rail fixed guideway systems : state safety oversight : final rule

DOT National Transportation Integrated Search

1995-12-27

As required by the Intermodal Surface Transportation Efficiency Act of 1991, the Federal Transit Administration (FTA) issues a rule requiring states to oversee the safety of rail fixed guideway systems not regulated by the Federal Railroad Administra...

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).

Inorganic Surface Coating with Fast Wetting-Dewetting Transitions for Liquid Manipulations.

PubMed

Yang, Yajie; Zhang, Liaoliao; Wang, Jue; Wang, Xinwei; Duan, Libing; Wang, Nan; Xiao, Fajun; Xie, Yanbo; Zhao, Jianlin

2018-06-06

Liquid manipulation is a fundamental issue for microfluidics and miniaturized sensors. Fast wetting-state transitions by optical methods have proven being efficient for liquid manipulations by organic surface coatings, however rarely been achieved by using inorganic coatings. Here, we report a fast optical-induced wetting-state transition surface achieved by inorganic coating, enabling tens of second transitions for a wetting-dewetting cycle, shortened from an hour, as typically reported. Here, we demonstrate a gravity-driven microfluidic reactor and switch it to a mixer after a second-step exposure in a minimum of within 80 s of UV exposure. The fast wetting-dewetting transition surfaces enable the fast switchable or erasable smart surfaces for water collection, miniature chemical reaction, or sensing systems by using inorganic surface coatings.

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.

A Multi-Armed Bandit Approach to Following a Markov Chain

DTIC Science & Technology

2017-06-01

focus on the House to Café transition (p1,4). We develop a Multi-Armed Bandit approach for efficiently following this target, where each state takes the...and longitude (each state corresponding to a physical location and a small set of activities). The searcher would then apply our approach on this...the target’s transition probability and the true probability over time. Further, we seek to provide upper bounds (i.e., worst case bounds) on the

Indicators of ecosystem function identify alternate states in the sagebrush steppe.

PubMed

Kachergis, Emily; Rocca, Monique E; Fernandez-Gimenez, Maria E

2011-10-01

Models of ecosystem change that incorporate nonlinear dynamics and thresholds, such as state-and-transition models (STMs), are increasingly popular tools for land management decision-making. However, few models are based on systematic collection and documentation of ecological data, and of these, most rely solely on structural indicators (species composition) to identify states and transitions. As STMs are adopted as an assessment framework throughout the United States, finding effective and efficient ways to create data-driven models that integrate ecosystem function and structure is vital. This study aims to (1) evaluate the utility of functional indicators (indicators of rangeland health, IRH) as proxies for more difficult ecosystem function measurements and (2) create a data-driven STM for the sagebrush steppe of Colorado, USA, that incorporates both ecosystem structure and function. We sampled soils, plant communities, and IRH at 41 plots with similar clayey soils but different site histories to identify potential states and infer the effects of management practices and disturbances on transitions. We found that many IRH were correlated with quantitative measures of functional indicators, suggesting that the IRH can be used to approximate ecosystem function. In addition to a reference state that functions as expected for this soil type, we identified four biotically and functionally distinct potential states, consistent with the theoretical concept of alternate states. Three potential states were related to management practices (chemical and mechanical shrub treatments and seeding history) while one was related only to ecosystem processes (erosion). IRH and potential states were also related to environmental variation (slope, soil texture), suggesting that there are environmental factors within areas with similar soils that affect ecosystem dynamics and should be noted within STMs. Our approach generated an objective, data-driven model of ecosystem dynamics for rangeland management. Our findings suggest that the IRH approximate ecosystem processes and can distinguish between alternate states and communities and identify transitions when building data-driven STMs. Functional indicators are a simple, efficient way to create data-driven models that are consistent with alternate state theory. Managers can use them to improve current model-building methods and thus apply state-and-transition models more broadly for land management decision-making.

Optically induced metastability in Cu(In,Ga)Se 2

DOE PAGES

Jensen, S. A.; Kanevce, A.; Mansfield, L. M.; ...

2017-10-23

Cu(In,Ga)Se 2 (CIGS) is presently the most efficient thin-film photovoltaic technology with efficiencies exceeding 22%. An important factor impacting the efficiency is metastability, where material changes occur over timescales of up to weeks during light exposure. A previously proposed (V Se -V Cu ) divacancy model presents a widely accepted explanation. We present experimental evidence for the optically induced metastability transition and expand the divacancy model with first-principles calculations. Using photoluminescence excitation spectroscopy, we identify a sub-bandgap optical transition that severely deteriorates the carrier lifetime. This is in accordance with the expanded divacancy model, which predicts that states below themore » conduction band are responsible for the metastability change. We determine the density–capture cross-section product of the induced lifetime-limiting states and evaluate their impact on device performance. The experimental and theoretical findings presented can allow assessment of metastability characteristics of leading thin-film photovoltaic technologies.« less

A comparison of operational performance : Washington state ferries to ferry operators worldwide.

DOT National Transportation Integrated Search

2010-06-01

This project compares eight measures of performance related to transit service quality (e.g. trip reliability, on-time departures) and cost-efficiency (e.g. farebox recovery, subsidy per passenger) between Washington State Ferries (WSF) and 23 ferry ...

A Simple test for the existence of two accretion modes in active galactic nuclei

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

Jester, Sebastian; /Fermilab

2005-02-01

By analogy to the different accretion states observed in black-hole X-ray binaries (BHXBs), it appears plausible that accretion disks in active galactic nuclei (AGN) undergo a state transition between a radiatively efficient and inefficient accretion flow. If the radiative efficiency changes at some critical accretion rate, there will be a change in the distribution of black hole masses and bolometric luminosities at the corresponding transition luminosity. To test this prediction, the author considers the joint distribution of AGN black hole masses and bolometric luminosities for a sample taken from the literature. The small number of objects with low Eddington-scaled accretionmore » rates m < 0.01 and black hole masses M{sub BH} < 10{sup 9} M{sub {circle_dot}} constitutes tentative evidence for the existence of such a transition in AGN. Selection effects, in particular those associated with flux-limited samples, systematically exclude objects in particular regions of the (M{sub BH}, L{sub bol}) plane. Therefore, they require particular attention in the analysis of distributions of black hole mass, bolometric luminosity, and derived quantities like the accretion rate. The author suggests further observational tests of the BHXB-AGN unification scheme which are based on the jet domination of the energy output of BHXBs in the hard state, and on the possible equivalence of BHXB in the very high (or steep power-law) state showing ejections and efficiently accreting quasars and radio galaxies with powerful radio jets.« less

Applications of neural networks to the studies of phase transitions of two-dimensional Potts models

NASA Astrophysics Data System (ADS)

Li, C.-D.; Tan, D.-R.; Jiang, F.-J.

2018-04-01

We study the phase transitions of two-dimensional (2D) Q-states Potts models on the square lattice, using the first principles Monte Carlo (MC) simulations as well as the techniques of neural networks (NN). We demonstrate that the ideas from NN can be adopted to study these considered phase transitions efficiently. In particular, even with a simple NN constructed in this investigation, we are able to obtain the relevant information of the nature of these phase transitions, namely whether they are first order or second order. Our results strengthen the potential applicability of machine learning in studying various states of matters. Subtlety of applying NN techniques to investigate many-body systems is briefly discussed as well.

Phase Transitions in a Model for Social Learning via the Internet

NASA Astrophysics Data System (ADS)

Bordogna, Clelia M.; Albano, Ezequiel V.

Based on the concepts of educational psychology, sociology and statistical physics, a mathematical model for a new type of social learning process that takes place when individuals interact via the Internet is proposed and studied. The noise of the interaction (misunderstandings, lack of well organized participative activities, etc.) dramatically restricts the number of individuals that can be efficiently in mutual contact and drives phase transitions between ``ordered states'' such as the achievements of the individuals are satisfactory and ``disordered states'' with negligible achievements.

Rotaxane liquid crystals with variable length: The effect of switching efficiency on the isotropic-nematic transition

NASA Astrophysics Data System (ADS)

He, Hao; Sevick, Edith M.; Williams, David R. M.

2018-04-01

We examine a solution of non-adaptive two-state rotaxane molecules which can switch from a short state of length L to a long state of length qL, using statistical thermodynamics. This molecular switching is externally driven and can result in an isotropic-nematic phase transition without altering temperature and concentration. Here we concentrate on the limitation imposed by switching inefficiency, i.e., on the case where molecular switching is not quantitative, leading to a solution of rotaxanes in different states. We present switching diagrams that can guide in the design of rotaxanes which affect a macroscopic phase change.

Facilitating a Major Staffing Transition in a State Psychiatric Hospital With Changes to Nursing Orientation.

PubMed

Birnbaum, Shira; Sperber-Weiss, Doreen; Dimitrios, Timothy; Eckel, Donald; Monroy-Miller, Cherry; Monroe, Janet J; Friedman, Ross; Ologbosele, Mathias; Epo, Grace; Sharpe, Debra; Zarski, Yongsuk

A large state psychiatric hospital experienced a state-mandated Reduction in Force that resulted in the abrupt loss and rapid turnover of more than 40% of its nursing and paraprofessional staff. The change exemplified current national trends toward downsizing and facility closure. This article describes revisions to the nursing orientation program that supported cost containment and fidelity to mission and clinical practices during the transition. An existing nursing orientation program was reconfigured in alignment with principles of rational instructional design and a core-competencies model of curriculum development, evidence-based practices that provided tactical clarity and commonality of purpose during a complex and emotionally charged transition period. Program redesign enabled efficiencies that facilitated the transition, with no evidence of associated negative effects. The process described here offers an example for hospitals facing similar workforce reorganization in an era of public sector downsizing.

Exact analytical solution of irreversible binary dynamics on networks.

PubMed

Laurence, Edward; Young, Jean-Gabriel; Melnik, Sergey; Dubé, Louis J

2018-03-01

In binary cascade dynamics, the nodes of a graph are in one of two possible states (inactive, active), and nodes in the inactive state make an irreversible transition to the active state, as soon as their precursors satisfy a predetermined condition. We introduce a set of recursive equations to compute the probability of reaching any final state, given an initial state, and a specification of the transition probability function of each node. Because the naive recursive approach for solving these equations takes factorial time in the number of nodes, we also introduce an accelerated algorithm, built around a breath-first search procedure. This algorithm solves the equations as efficiently as possible in exponential time.

Exact analytical solution of irreversible binary dynamics on networks

NASA Astrophysics Data System (ADS)

Laurence, Edward; Young, Jean-Gabriel; Melnik, Sergey; Dubé, Louis J.

2018-03-01

In binary cascade dynamics, the nodes of a graph are in one of two possible states (inactive, active), and nodes in the inactive state make an irreversible transition to the active state, as soon as their precursors satisfy a predetermined condition. We introduce a set of recursive equations to compute the probability of reaching any final state, given an initial state, and a specification of the transition probability function of each node. Because the naive recursive approach for solving these equations takes factorial time in the number of nodes, we also introduce an accelerated algorithm, built around a breath-first search procedure. This algorithm solves the equations as efficiently as possible in exponential time.

Improved efficiency of selective photoionization of palladium isotopes via autoionizing Rydberg states

NASA Astrophysics Data System (ADS)

Locke, Clayton R.; Kobayashi, Tohru; Midorikawa, Katsumi

2017-01-01

Odd-mass-selective ionization of palladium for purposes of resource recycling and management of long-lived fission products can be achieved by exploiting transition selection rules in a well-established three-step excitation process. In this conventional scheme, circularly polarized lasers of the same handedness excite isotopes via two intermediate 2D5/2 core states, and a third laser is then used for ionization via autoionizing Rydberg states. We propose an alternative excitation scheme via intermediate 2D3/2 core states before the autoionizing Rydberg state, improving ionization efficiency by over 130 times. We confirm high selectivity and measure odd-mass isotopes of >99.7(3)% of the total ionized product. We have identified and measured the relative ionization efficiency of the series of Rydberg states that converge to upper ionization limit of the 4 d 9(2D3/2) level, and identify the most efficient excitation is via the Rydberg state at 67668.18(10) cm-1.

Structure-guided Protein Transition Modeling with a Probabilistic Roadmap Algorithm.

PubMed

Maximova, Tatiana; Plaku, Erion; Shehu, Amarda

2016-07-07

Proteins are macromolecules in perpetual motion, switching between structural states to modulate their function. A detailed characterization of the precise yet complex relationship between protein structure, dynamics, and function requires elucidating transitions between functionally-relevant states. Doing so challenges both wet and dry laboratories, as protein dynamics involves disparate temporal scales. In this paper we present a novel, sampling-based algorithm to compute transition paths. The algorithm exploits two main ideas. First, it leverages known structures to initialize its search and define a reduced conformation space for rapid sampling. This is key to address the insufficient sampling issue suffered by sampling-based algorithms. Second, the algorithm embeds samples in a nearest-neighbor graph where transition paths can be efficiently computed via queries. The algorithm adapts the probabilistic roadmap framework that is popular in robot motion planning. In addition to efficiently computing lowest-cost paths between any given structures, the algorithm allows investigating hypotheses regarding the order of experimentally-known structures in a transition event. This novel contribution is likely to open up new venues of research. Detailed analysis is presented on multiple-basin proteins of relevance to human disease. Multiscaling and the AMBER ff14SB force field are used to obtain energetically-credible paths at atomistic detail.

High energy efficient solid state laser sources

NASA Technical Reports Server (NTRS)

Byer, Robert L.

1987-01-01

Diode-laser-pumped solid-state laser oscillators and nonlinear processes were investigated. A new generation on nonplanar oscillator was fabricated, and it is anticipated that passive linewidths will be pushed to the kilohertz regime. A number of diode-pumped laser transitions were demonstrated in the rod configuration. Second-harmonic conversion efficiencies as high as 15% are routinely obtained in a servo-locked external resonant doubling crystal at 15 mW cw input power levels at 1064 nm.

Maximum efficiency of state-space models of nanoscale energy conversion devices

NASA Astrophysics Data System (ADS)

Einax, Mario; Nitzan, Abraham

2016-07-01

The performance of nano-scale energy conversion devices is studied in the framework of state-space models where a device is described by a graph comprising states and transitions between them represented by nodes and links, respectively. Particular segments of this network represent input (driving) and output processes whose properly chosen flux ratio provides the energy conversion efficiency. Simple cyclical graphs yield Carnot efficiency for the maximum conversion yield. We give general proof that opening a link that separate between the two driving segments always leads to reduced efficiency. We illustrate these general result with simple models of a thermoelectric nanodevice and an organic photovoltaic cell. In the latter an intersecting link of the above type corresponds to non-radiative carriers recombination and the reduced maximum efficiency is manifested as a smaller open-circuit voltage.

Maximum efficiency of state-space models of nanoscale energy conversion devices.

PubMed

Einax, Mario; Nitzan, Abraham

2016-07-07

The performance of nano-scale energy conversion devices is studied in the framework of state-space models where a device is described by a graph comprising states and transitions between them represented by nodes and links, respectively. Particular segments of this network represent input (driving) and output processes whose properly chosen flux ratio provides the energy conversion efficiency. Simple cyclical graphs yield Carnot efficiency for the maximum conversion yield. We give general proof that opening a link that separate between the two driving segments always leads to reduced efficiency. We illustrate these general result with simple models of a thermoelectric nanodevice and an organic photovoltaic cell. In the latter an intersecting link of the above type corresponds to non-radiative carriers recombination and the reduced maximum efficiency is manifested as a smaller open-circuit voltage.

Gene expression in bovine rumen epithelium during weaning indentifies molecular regulators of rumen development and growth

USDA-ARS?s Scientific Manuscript database

During weaning, rumen epithelial cell function must transition from a pre-ruminant to a true ruminant state for efficient nutrient absorption and metabolism. During this time, the rumen increases from 30 to 70% of the capacity of the gut, significantly impacting net efficiency of feed conversion in ...

Characterization of differentially expressed genes in calf rumen epithelium in response to weaning

USDA-ARS?s Scientific Manuscript database

During weaning, rumen epithelial cell function must transition from a pre-ruminant to a true ruminant state for efficient nutrient absorption and metabolism. During this time, the rumen grows to represent from 30 to 70% of the capacity of the gut, directly impacting net efficiency of feed conversion...

Adaptive particle filter for robust visual tracking

NASA Astrophysics Data System (ADS)

Dai, Jianghua; Yu, Shengsheng; Sun, Weiping; Chen, Xiaoping; Xiang, Jinhai

2009-10-01

Object tracking plays a key role in the field of computer vision. Particle filter has been widely used for visual tracking under nonlinear and/or non-Gaussian circumstances. In particle filter, the state transition model for predicting the next location of tracked object assumes the object motion is invariable, which cannot well approximate the varying dynamics of the motion changes. In addition, the state estimate calculated by the mean of all the weighted particles is coarse or inaccurate due to various noise disturbances. Both these two factors may degrade tracking performance greatly. In this work, an adaptive particle filter (APF) with a velocity-updating based transition model (VTM) and an adaptive state estimate approach (ASEA) is proposed to improve object tracking. In APF, the motion velocity embedded into the state transition model is updated continuously by a recursive equation, and the state estimate is obtained adaptively according to the state posterior distribution. The experiment results show that the APF can increase the tracking accuracy and efficiency in complex environments.

The relation between the quantum discord and quantum teleportation: The physical interpretation of the transition point between different quantum discord decay regimes

NASA Astrophysics Data System (ADS)

Roszak, K.; Cywiński, Ł.

2015-10-01

We study quantum teleportation via Bell-diagonal mixed states of two qubits in the context of the intrinsic properties of the quantum discord. We show that when the quantum-correlated state of the two qubits is used for quantum teleportation, the character of the teleportation efficiency changes substantially depending on the Bell-diagonal-state parameters, which can be seen when the worst-case-scenario or best-case-scenario fidelity is studied. Depending on the parameter range, one of two types of single-qubit states is hardest/easiest to teleport. The transition between these two parameter ranges coincides exactly with the transition between the range of classical correlation decay and quantum correlation decay characteristic for the evolution of the quantum discord. The correspondence provides a physical interpretation for the prominent feature of the decay of the quantum discord.

Vibrational energy transfer dynamics in ruthenium polypyridine transition metal complexes.

PubMed

Fedoseeva, Marina; Delor, Milan; Parker, Simon C; Sazanovich, Igor V; Towrie, Michael; Parker, Anthony W; Weinstein, Julia A

2015-01-21

Understanding the dynamics of the initial stages of vibrational energy transfer in transition metal complexes is a challenging fundamental question which is also of crucial importance for many applications, such as improving the performance of solar devices or photocatalysis. The present study investigates vibrational energy transport in the ground and the electronic excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2, a close relative of the efficient "N3" dye used in dye-sensitized solar cells. Using the emerging technique of ultrafast two-dimensional infrared spectroscopy, we show that, similarly to other transition-metal complexes, the central Ru heavy atom acts as a "bottleneck" making the energy transfer from small ligands with high energy vibrational stretching frequencies less favorable and thereby affecting the efficiency of vibrational energy flow in the complex. Comparison of the vibrational relaxation times in the electronic ground and excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2 shows that it is dramatically faster in the latter. We propose to explain this observation by the intramolecular electrostatic interactions between the thiocyanate group and partially oxidised Ru metal center, which increase the degree of vibrational coupling between CN and Ru-N modes in the excited state thus reducing structural and thermodynamic barriers that slow down vibrational relaxation and energy transport in the electronic ground state. As a very similar behavior was earlier observed in another transition-metal complex, Re(4,4'-(COOEt)2-2,2'-bpy)(CO)3Cl, we suggest that this effect in vibrational energy dynamics might be common for transition-metal complexes with heavy central atoms.

Reconfiguration of a smart surface using heteroclinic connections

PubMed Central

McInnes, Colin R.; Xu, Ming

2017-01-01

A reconfigurable smart surface with multiple equilibria is presented, modelled using discrete point masses and linear springs with geometric nonlinearity. An energy-efficient reconfiguration scheme is then investigated to connect equal-energy unstable (but actively controlled) equilibria. In principle, zero net energy input is required to transition the surface between these unstable states, compared to transitions between stable equilibria across a potential barrier. These transitions between equal-energy unstable states, therefore, form heteroclinic connections in the phase space of the problem. Moreover, the smart surface model developed can be considered as a unit module for a range of applications, including modules which can aggregate together to form larger distributed smart surface systems. PMID:28265191

Fast optical cooling of nanomechanical cantilever with the dynamical Zeeman effect.

PubMed

Zhang, Jian-Qi; Zhang, Shuo; Zou, Jin-Hua; Chen, Liang; Yang, Wen; Li, Yong; Feng, Mang

2013-12-02

We propose an efficient optical electromagnetically induced transparency (EIT) cooling scheme for a cantilever with a nitrogen-vacancy center attached in a non-uniform magnetic field using dynamical Zeeman effect. In our scheme, the Zeeman effect combined with the quantum interference effect enhances the desired cooling transition and suppresses the undesired heating transitions. As a result, the cantilever can be cooled down to nearly the vibrational ground state under realistic experimental conditions within a short time. This efficient optical EIT cooling scheme can be reduced to the typical EIT cooling scheme under special conditions.

Solid-state rechargeable magnesium battery

DOEpatents

Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

2016-09-06

Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

Evidence and mechanism of efficient thermally activated delayed fluorescence promoted by delocalized excited states

PubMed Central

Hosokai, Takuya; Matsuzaki, Hiroyuki; Nakanotani, Hajime; Tokumaru, Katsumi; Tsutsui, Tetsuo; Furube, Akihiro; Nasu, Keirou; Nomura, Hiroko; Yahiro, Masayuki; Adachi, Chihaya

2017-01-01

The design of organic compounds with nearly no gap between the first excited singlet (S1) and triplet (T1) states has been demonstrated to result in an efficient spin-flip transition from the T1 to S1 state, that is, reverse intersystem crossing (RISC), and facilitate light emission as thermally activated delayed fluorescence (TADF). However, many TADF molecules have shown that a relatively appreciable energy difference between the S1 and T1 states (~0.2 eV) could also result in a high RISC rate. We revealed from a comprehensive study of optical properties of TADF molecules that the formation of delocalized states is the key to efficient RISC and identified a chemical template for these materials. In addition, simple structural confinement further enhances RISC by suppressing structural relaxation in the triplet states. Our findings aid in designing advanced organic molecules with a high rate of RISC and, thus, achieving the maximum theoretical electroluminescence efficiency in organic light-emitting diodes. PMID:28508081

Disruption of the ndhF1 gene affects Chl fluorescence through state transition in the Cyanobacterium Synechocystis sp. PCC 6803, resulting in apparent high efficiency of photosynthesis.

PubMed

Ogawa, Takako; Harada, Tetsuyuki; Ozaki, Hiroshi; Sonoike, Kintake

2013-07-01

In Synechocystis sp. PCC 6803, the disruption of the ndhF1 gene (slr0844), which encodes a subunit of one of the NDH-1 complexes (NDH-1L complex) serving for respiratory electron transfer, causes the largest change in Chl fluorescence induction kinetics among the kinetics of 750 disruptants searched in the Fluorome, the cyanobacterial Chl fluorescence database. The cause of the explicit phenotype of the ndhF1 disruptant was examined by measurements of the photosynthetic rate, Chl fluorescence and state transition. The results demonstrate that the defects in respiratory electron transfer obviously have great impact on Chl fluorescence in cyanobacteria. The inactivation of NDH-1L complexes involving electron transfer from NDH-1 to plastoquinone (PQ) would result in the oxidation of the PQ pool, leading to the transition to State 1, where the yield of Chl fluorescence is high. Apparently, respiration, although its rate is far lower than that of photosynthesis, could affect Chl fluorescence through the state transition as leverage. The disruption of the ndhF1 gene caused lower oxygen-evolving activity but the estimated electron transport rate from Chl fluorescence measurements was faster in the mutant than in the wild-type cells. The discrepancy could be ascribed to the decreased level of non-photochemical quenching due to state transition. One must be cautious when using the Chl fluorescence parameter to estimate photosynthesis in mutants defective in state transition.

Highly efficient near ultraviolet organic light-emitting diode based on a meta-linked donor–acceptor molecule† †Electronic supplementary information (ESI) available: The details of the synthesis; the ground state and excited state geometries in PPI, TPA–PPI and mTPA–PPI; absorption and emission properties of PPI, TPA–PPI and mTPA–PPI in the gas phase; detailed absorption peak positions, emission peak positions and ηPL values of PPI and mTPA–PPI in different solvents; HOMO and LUMO of mTPA–PPI at ground state; NTO for the S0 → S1 absorption transition in PPI, TPA–PPI and mTPA–PPI; NTO for S0 → Sn electronic transition character in mTPA–PPI; lifetime measurement, radiative transition rates and non-radiative transition rates of PPI and mTPA–PPI in hexane and THF solutions; low-temperature fluorescence and phosphorescence spectra of PPI and mTPA–PPI; CV curves of PPI and mTPA–PPI, and schematic diagram of design principle of mTPA–PPI; TGA and DSC graphs of PPI and mTPA–PPI; current efficiency–current density–power efficiency curves and EL spectra at different driving voltages of PPI and mTPA–PPI devices. See DOI: 10.1039/c5sc01131k

PubMed Central

Liu, Haichao; Bai, Qing; Yao, Liang; Zhang, Haiyan; Xu, Hai; Zhang, Shitong; Li, Weijun; Gao, Yu; Li, Jinyu; Lu, Ping; Wang, Hongyan; Ma, Yuguang

2015-01-01

A novel near ultraviolet (NUV) emitter with a meta-linked donor–acceptor (D–A) structure between triphenylamine (TPA) and phenanthroimidazole (PPI), mTPA–PPI, was designed and synthesized. This molecular design is expected to resolve the conflict between the non-red-shifted emission and the introduction of a charge-transfer (CT) state in the D–A system, aiming at NUV organic light-emitting diodes (OLEDs) with high-efficiency and colour-purity. Theoretical calculations and photophysical experiments were implemented to verify the unique excited state properties of mTPA–PPI. The mTPA–PPI device exhibited excellent NUV electroluminescence (EL) performance with an emission peak at 404 nm, a full width at half maximum (FWHM) of only 47 nm corresponding to a CIE coordinate of (0.161, 0.049), and a maximum external quantum efficiency (EQE) of 3.33%, which is among the best results for NUV OLEDs. This work not only demonstrates the promising potential of mTPA–PPI in NUV OLEDs, but also provides a valuable strategy for the rational design of NUV materials by using the meta-linked D–A architecture. PMID:29218149

Cell population structure prior to bifurcation predicts efficiency of directed differentiation in human induced pluripotent cells

PubMed Central

Bargaje, Rhishikesh; Trachana, Kalliopi; Shelton, Martin N.; McGinnis, Christopher S.; Zhou, Joseph X.; Chadick, Cora; Cook, Savannah; Cavanaugh, Christopher; Huang, Sui; Hood, Leroy

2017-01-01

Steering the differentiation of induced pluripotent stem cells (iPSCs) toward specific cell types is crucial for patient-specific disease modeling and drug testing. This effort requires the capacity to predict and control when and how multipotent progenitor cells commit to the desired cell fate. Cell fate commitment represents a critical state transition or “tipping point” at which complex systems undergo a sudden qualitative shift. To characterize such transitions during iPSC to cardiomyocyte differentiation, we analyzed the gene expression patterns of 96 developmental genes at single-cell resolution. We identified a bifurcation event early in the trajectory when a primitive streak-like cell population segregated into the mesodermal and endodermal lineages. Before this branching point, we could detect the signature of an imminent critical transition: increase in cell heterogeneity and coordination of gene expression. Correlation analysis of gene expression profiles at the tipping point indicates transcription factors that drive the state transition toward each alternative cell fate and their relationships with specific phenotypic readouts. The latter helps us to facilitate small molecule screening for differentiation efficiency. To this end, we set up an analysis of cell population structure at the tipping point after systematic variation of the protocol to bias the differentiation toward mesodermal or endodermal cell lineage. We were able to predict the proportion of cardiomyocytes many days before cells manifest the differentiated phenotype. The analysis of cell populations undergoing a critical state transition thus affords a tool to forecast cell fate outcomes and can be used to optimize differentiation protocols to obtain desired cell populations. PMID:28167799

Cell population structure prior to bifurcation predicts efficiency of directed differentiation in human induced pluripotent cells.

PubMed

Bargaje, Rhishikesh; Trachana, Kalliopi; Shelton, Martin N; McGinnis, Christopher S; Zhou, Joseph X; Chadick, Cora; Cook, Savannah; Cavanaugh, Christopher; Huang, Sui; Hood, Leroy

2017-02-28

Steering the differentiation of induced pluripotent stem cells (iPSCs) toward specific cell types is crucial for patient-specific disease modeling and drug testing. This effort requires the capacity to predict and control when and how multipotent progenitor cells commit to the desired cell fate. Cell fate commitment represents a critical state transition or "tipping point" at which complex systems undergo a sudden qualitative shift. To characterize such transitions during iPSC to cardiomyocyte differentiation, we analyzed the gene expression patterns of 96 developmental genes at single-cell resolution. We identified a bifurcation event early in the trajectory when a primitive streak-like cell population segregated into the mesodermal and endodermal lineages. Before this branching point, we could detect the signature of an imminent critical transition: increase in cell heterogeneity and coordination of gene expression. Correlation analysis of gene expression profiles at the tipping point indicates transcription factors that drive the state transition toward each alternative cell fate and their relationships with specific phenotypic readouts. The latter helps us to facilitate small molecule screening for differentiation efficiency. To this end, we set up an analysis of cell population structure at the tipping point after systematic variation of the protocol to bias the differentiation toward mesodermal or endodermal cell lineage. We were able to predict the proportion of cardiomyocytes many days before cells manifest the differentiated phenotype. The analysis of cell populations undergoing a critical state transition thus affords a tool to forecast cell fate outcomes and can be used to optimize differentiation protocols to obtain desired cell populations.

Optical properties of InAs/GaAs quantum dot superlattice structures

NASA Astrophysics Data System (ADS)

Imran, Ali; Jiang, Jianliang; Eric, Deborah; Zahid, M. Noaman; Yousaf, M.; Shah, Z. H.

2018-06-01

Quantum dot (QD) structure has potential applications in modern highly efficient optoelectronic devices due to their band-tuning. The device dimensions have been miniatured with increased efficiencies by virtue of this discovery. In this research, we have presented modified analytical and simulation results of InAs/GaAs QD superlattice (QDSL). We have applied tight binding model for the investigation of ground state energies using timeindependent Schrödinger equation (SE) with effective mass approximation. It has been investigated that the electron energies are confined due to wave function delocalization in closely coupled QD structures. The minimum ground state energy can be obtained by increasing the periodicity and decreasing the barrier layer thickness. We have calculated electronics and optical properties which includes ground state energies, transition energies, density of states (DOS), absorption coefficient and refractive index, which can be tuned by structure modification. In our results, the minimum ground state energy of QDSL is achieved to be 0.25 eV with a maximum period of 10 QDs. The minimum band to band and band to continuum transition energies are 63 meV and 130 meV with 2 nm barrier layer thickness respectively. The absorption coefficient of our proposed QDSL model is found to be maximum 1.2 × 104 cm-1 and can be used for highly sensitive infrared detector and high efficiency solar cells.

A one-way shooting algorithm for transition path sampling of asymmetric barriers

NASA Astrophysics Data System (ADS)

Brotzakis, Z. Faidon; Bolhuis, Peter G.

2016-10-01

We present a novel transition path sampling shooting algorithm for the efficient sampling of complex (biomolecular) activated processes with asymmetric free energy barriers. The method employs a fictitious potential that biases the shooting point toward the transition state. The method is similar in spirit to the aimless shooting technique by Peters and Trout [J. Chem. Phys. 125, 054108 (2006)], but is targeted for use with the one-way shooting approach, which has been shown to be more effective than two-way shooting algorithms in systems dominated by diffusive dynamics. We illustrate the method on a 2D Langevin toy model, the association of two peptides and the initial step in dissociation of a β-lactoglobulin dimer. In all cases we show a significant increase in efficiency.

Spectroscopic Studies on Unfolding Processes of Apo-Neuroglobin Induced by Guanidine Hydrochloride and Urea

PubMed Central

Zhang, Cui; Gao, Chaohui; Qiu, Zhanglei

2013-01-01

Neuroglobin (Ngb), a recently discovered globin, is predominantly expressed in the brain, retina, and other nerve tissues of vertebrates. The unfolding processes of apo-neuroglobin (apoNgb) induced by guanidine hydrochloride (GdnHCl) and urea were investigated by spectroscopic methods. In the unfolding processes, apoNgb's tertiary structural transition was monitored by the changes of intrinsic fluorescence emission spectra, and its secondary structural transition was measured by the changes of far-ultraviolet circular dichroism (CD) spectra. In addition, 8-anilino-1-naphthalenesulfonic acid (ANS), a hydrophobic cluster binding dye, was also used to monitor the unfolding process of apoNgb and to explore its intermediates. Results showed that GdnHCl-induced unfolding of apoNgb was via a three-state pathway, that is, Native state (N) → Intermediate state (I) → Unfolded state (U), during which the intermediate was inferred by an increase in fluorescence intensity and the change of CD value. Gibbs free energy changes are 10.2 kJ·mol−1 for the first unfolding transition and 14.0 kJ·mol−1 for the second transition. However, urea-induced unfolding of apoNgb only underwent a two-state transition: Native state (N) → Partially unfolded state (P). The result showed that GdnHCl can efficiently affect the conformational states of apoNgb compared with those of urea. The work will benefit to have an understanding of the unfolding mechanism of apoNgb induced by GdnHCl and urea. PMID:23984347

Charge Separation and Exciton Dynamics at Polymer/ZnO Interface from First-Principles Simulations.

PubMed

Wu, Guangfen; Li, Zi; Zhang, Xu; Lu, Gang

2014-08-07

Charge separation and exciton dynamics play a crucial role in determining the performance of excitonic photovoltaics. Using time-dependent density functional theory with a range-separated exchange-correlation functional as well as nonadiabatic ab initio molecular dynamics, we have studied the formation and dynamics of charge-transfer (CT) excitons at polymer/ZnO interface. The interfacial atomic structure, exciton density of states and conversions between exciton species are examined from first-principles. The exciton dynamics exhibits both adiabatic and nonadiabatic characters. While the adiabatic transitions are facilitated by C═C vibrations along the polymer (P3HT) backbone, the nonadiabatic transitions are realized by exciton hopping between the excited states. We find that the localized ZnO surface states lead to localized low-energy CT states and poor charge separation. In contrast, the surface states of crystalline C60 are indistinguishable from the bulk states, resulting in delocalized CT states and efficient charge separation in polymer/fullerene (P3HT/PCBM) heterojunctions. The hot CT states are found to cool down in an ultrafast time scale and may not play a major role in charge separation of P3HT/ZnO. Finally we suggest that the dimensions of nanostructured acceptors can be tuned to obtain both efficient charge separation and high open circuit voltages.

Speculation and replication in temperature accelerated dynamics

DOE PAGES

Zamora, Richard J.; Perez, Danny; Voter, Arthur F.

2018-02-12

Accelerated Molecular Dynamics (AMD) is a class of MD-based algorithms for the long-time scale simulation of atomistic systems that are characterized by rare-event transitions. Temperature-Accelerated Dynamics (TAD), a traditional AMD approach, hastens state-to-state transitions by performing MD at an elevated temperature. Recently, Speculatively-Parallel TAD (SpecTAD) was introduced, allowing the TAD procedure to exploit parallel computing systems by concurrently executing in a dynamically generated list of speculative future states. Although speculation can be very powerful, it is not always the most efficient use of parallel resources. In this paper, we compare the performance of speculative parallelism with a replica-based technique, similarmore » to the Parallel Replica Dynamics method. A hybrid SpecTAD approach is also presented, in which each speculation process is further accelerated by a local set of replicas. Finally and overall, this work motivates the use of hybrid parallelism whenever possible, as some combination of speculation and replication is typically most efficient.« less

Speculation and replication in temperature accelerated dynamics

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

Zamora, Richard J.; Perez, Danny; Voter, Arthur F.

Accelerated Molecular Dynamics (AMD) is a class of MD-based algorithms for the long-time scale simulation of atomistic systems that are characterized by rare-event transitions. Temperature-Accelerated Dynamics (TAD), a traditional AMD approach, hastens state-to-state transitions by performing MD at an elevated temperature. Recently, Speculatively-Parallel TAD (SpecTAD) was introduced, allowing the TAD procedure to exploit parallel computing systems by concurrently executing in a dynamically generated list of speculative future states. Although speculation can be very powerful, it is not always the most efficient use of parallel resources. In this paper, we compare the performance of speculative parallelism with a replica-based technique, similarmore » to the Parallel Replica Dynamics method. A hybrid SpecTAD approach is also presented, in which each speculation process is further accelerated by a local set of replicas. Finally and overall, this work motivates the use of hybrid parallelism whenever possible, as some combination of speculation and replication is typically most efficient.« less

Directed emission of CdSe nanoplatelets originating from strongly anisotropic 2D electronic structure

NASA Astrophysics Data System (ADS)

Scott, Riccardo; Heckmann, Jan; Prudnikau, Anatol V.; Antanovich, Artsiom; Mikhailov, Aleksandr; Owschimikow, Nina; Artemyev, Mikhail; Climente, Juan I.; Woggon, Ulrike; Grosse, Nicolai B.; Achtstein, Alexander W.

2017-12-01

Intrinsically directional light emitters are potentially important for applications in photonics including lasing and energy-efficient display technology. Here, we propose a new route to overcome intrinsic efficiency limitations in light-emitting devices by studying a CdSe nanoplatelets monolayer that exhibits strongly anisotropic, directed photoluminescence. Analysis of the two-dimensional k-space distribution reveals the underlying internal transition dipole distribution. The observed directed emission is related to the anisotropy of the electronic Bloch states governing the exciton transition dipole moment and forming a bright plane. The strongly directed emission perpendicular to the platelet is further enhanced by the optical local density of states and local fields. In contrast to the emission directionality, the off-resonant absorption into the energetically higher 2D-continuum of states is isotropic. These contrasting optical properties make the oriented CdSe nanoplatelets, or superstructures of parallel-oriented platelets, an interesting and potentially useful class of semiconductor-based emitters.

Two-Photon Transitions in Hydrogen-Like Atoms

NASA Astrophysics Data System (ADS)

Martinis, Mladen; Stojić, Marko

Different methods for evaluating two-photon transition amplitudes in hydrogen-like atoms are compared with the improved method of direct summation. Three separate contributions to the two-photon transition probabilities in hydrogen-like atoms are calculated. The first one coming from the summation over discrete intermediate states is performed up to nc(max) = 35. The second contribution from the integration over the continuum states is performed numerically. The third contribution coming from the summation from nc(max) to infinity is calculated in an approximate way using the mean level energy for this region. It is found that the choice of nc(max) controls the numerical error in the calculations and can be used to increase the accuracy of the results much more efficiently than in other methods.

A System of Systems (SoS) Approach to transforming to a low carbon resource-efficient energy system: Insights for the European Union (EU)

NASA Astrophysics Data System (ADS)

Madani, K.; Jess, T.; Mahlooji, M.; Ristic, B.

2015-12-01

The world's energy sector is experiencing a serious transition from reliance on fossil fuel energy sources to extensive reliance on renewable energies. Europe is leading the way in this transition to a low carbon economy in an attempt to keep climate change below 2oC. Member States have committed themselves to reducing greenhouse gas emissions by 20% and increasing the share of renewables in the EU's energy mix to 20% by 2020. The EU has now gone a step further with the objective of reducing greenhouse gas emissions by 80-95% by 2050. Nevertheless, the short-term focus of the European Commission is at "cost-efficient ways" to cut its greenhouse gas emissions which forgoes the unintended impacts of a large expansion of low-carbon energy technologies on major natural resources such as water and land. This study uses the "System of Systems (SoS) Approach to Energy Sustainability Assessment" (Hadian and Madani, 2015) to evaluate the Relative Aggregate Footprint (RAF) of energy sources in different European Union (EU) member states. RAF reflects the overall resource-use efficiency of energy sources with respect to four criteria: carbon footprint, water footprint, land footprint, and economic cost. Weights are assigned to the four resource use efficiency criteria based on each member state's varying natural and economic resources to examine the changes in the desirability of energy sources based on regional resource availability conditions, and to help evaluating the overall resource use efficiency of the EU's energy portfolio. A longer-term strategy in Europe has been devised under the "Resource Efficient Europe" flagship imitative intended to put the EU on course to using resources in a sustainable way. This study will highlight the resource efficiency of the EU's energy sector in order to assist in a sustainable transition to a low carbon economy in Europe. ReferenceHadian S, Madani K (2015) A System of Systems Approach to Energy Sustainability Assessment: Are All Renewables Really Green? Ecological Indicators, 52, 194-206.

Models of charge pair generation in organic solar cells.

PubMed

Few, Sheridan; Frost, Jarvist M; Nelson, Jenny

2015-01-28

Efficient charge pair generation is observed in many organic photovoltaic (OPV) heterojunctions, despite nominal electron-hole binding energies which greatly exceed the average thermal energy. Empirically, the efficiency of this process appears to be related to the choice of donor and acceptor materials, the resulting sequence of excited state energy levels and the structure of the interface. In order to establish a suitable physical model for the process, a range of different theoretical studies have addressed the nature and energies of the interfacial states, the energetic profile close to the heterojunction and the dynamics of excited state transitions. In this paper, we review recent developments underpinning the theory of charge pair generation and phenomena, focussing on electronic structure calculations, electrostatic models and approaches to excited state dynamics. We discuss the remaining challenges in achieving a predictive approach to charge generation efficiency.

Control of diastereoselectivity by solvent effects in the addition of Grignard reagents to enantiopure t-butylsulfinimine: syntheses of the stereoisomers of the hydroxyl derivatives of sibutramine.

PubMed

Lu, Bruce Z; Senanayake, Chris; Li, Nansheng; Han, Zhengxu; Bakale, Roger P; Wald, Stephen A

2005-06-23

[reaction: see text] An efficient method has been developed to prepare all four isomers of the hydroxyl derivatives of sibutramine by addition of Grignard reagents (R)- or (S)-5 to a single enantiomer of sulfinyl imine (R)-1 simply by tuning the reaction solvent. The phenomenon of the reversed diastereoselectivity in CH(2)Cl(2) and THF implied that the reaction may proceed through a chelated cyclic transition state in CH(2)Cl(2) and nonchelated acyclic transition state in THF.

Graph transformation method for calculating waiting times in Markov chains.

PubMed

Trygubenko, Semen A; Wales, David J

2006-06-21

We describe an exact approach for calculating transition probabilities and waiting times in finite-state discrete-time Markov processes. All the states and the rules for transitions between them must be known in advance. We can then calculate averages over a given ensemble of paths for both additive and multiplicative properties in a nonstochastic and noniterative fashion. In particular, we can calculate the mean first-passage time between arbitrary groups of stationary points for discrete path sampling databases, and hence extract phenomenological rate constants. We present a number of examples to demonstrate the efficiency and robustness of this approach.

Transition-Tempered Metadynamics: Robust, Convergent Metadynamics via On-the-Fly Transition Barrier Estimation.

PubMed

Dama, James F; Rotskoff, Grant; Parrinello, Michele; Voth, Gregory A

2014-09-09

Well-tempered metadynamics has proven to be a practical and efficient adaptive enhanced sampling method for the computational study of biomolecular and materials systems. However, choosing its tunable parameter can be challenging and requires balancing a trade-off between fast escape from local metastable states and fast convergence of an overall free energy estimate. In this article, we present a new smoothly convergent variant of metadynamics, transition-tempered metadynamics, that removes that trade-off and is more robust to changes in its own single tunable parameter, resulting in substantial speed and accuracy improvements. The new method is specifically designed to study state-to-state transitions in which the states of greatest interest are known ahead of time, but transition mechanisms are not. The design is guided by a picture of adaptive enhanced sampling as a means to increase dynamical connectivity of a model's state space until percolation between all points of interest is reached, and it uses the degree of dynamical percolation to automatically tune the convergence rate. We apply the new method to Brownian dynamics on 48 random 1D surfaces, blocked alanine dipeptide in vacuo, and aqueous myoglobin, finding that transition-tempered metadynamics substantially and reproducibly improves upon well-tempered metadynamics in terms of first barrier crossing rate, convergence rate, and robustness to the choice of tuning parameter. Moreover, the trade-off between first barrier crossing rate and convergence rate is eliminated: the new method drives escape from an initial metastable state as fast as metadynamics without tempering, regardless of tuning.

Kinetics of First-Row Transition Metal Cations (V+, Fe+, Co+) with OCS at Thermal Energies.

PubMed

Sweeny, Brendan C; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A

2018-05-03

The temperature-dependent kinetics for reactions of V + , Fe + , and Co + with OCS are measured using a selected ion flow tube apparatus heated to 300-600 K. All three reactions proceed solely by C-S activation at thermal energies, resulting in metal sulfide cation formation. Previously calculated reaction pathways were employed to inform statistical modeling of these reactions for comparison to the data. As surmised previously, all three reactions at thermal energies require spin crossing, with the Fe + reaction crossing once circumventing a prohibitive transition state, before crossing again to form ground state products. The Fe + and Co + reaction efficiencies increase with energy. For the Co + reaction, and to a lesser extent the Fe + reaction, the apparent activation energies are less than the reaction endothermicities, possibly indicating increasing diabatic behavior of the spin crossings with energy. The V + reaction was well modeled assuming an entirely adiabatic spin crossing, such that the resultant avoided crossing behaves similarly to a tight transition state. The subsequent reaction of VS + with OCS producing VS 2 + is also investigated; the rate-limiting transition state energy derived from statistical modeling is poorly reproduced by quantum calculations using a variety of methods, highlighting the large (1-2 eV) uncertainty in calculated energetics of transition-metal containing species.

Development of Guidance for States Transitioning to New Safety Analysis Tools

ERIC Educational Resources Information Center

Alluri, Priyanka

2010-01-01

With about 125 people dying on US roads each day, the US Department of Transportation heightened the awareness of critical safety issues with the passage of SAFETEA-LU (Safe Accountable Flexible Efficient Transportation Equity Act--A Legacy for Users) legislation in 2005. The legislation required each of the states to develop a Strategic Highway…

Highly efficient saturated visible up-conversion photoluminescent Y 2 O 3 :Er 3+ microspheres pumped with a 1.55 μm laser diode

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

Zhao, Jinbo; Wu, Lili; Zhang, Chuanjiang

2017-01-01

Highly efficient saturation up-conversion (UC) luminescent Y2O3:Er3+ microspheres have been successfully prepared via a hydrothermal-homogeneous precipitation method. Bright visible luminescence can be clearly seen with a 1.55 mu m laser diode excitation power as low as similar to 0.03 W cm(-2). The up-conversion (UC) emission spectra indicate that the strongest red emission with a peak situated at similar to 660 nm originated from the I-4(9/2) -> I-4(15/2) transition of Er3+. The peaks situated at similar to 520 and 550 nm can be assigned to the transition from H-2(11/2)/S-4(3/2) state to the ground state of Er3+. The high efficient saturation up-conversionmore » emission is related to the highly crystalline structure. These results indicate a new way to enhance UC radiation in rare-earth ion-doped materials prepared using a hydrothermal-homogeneous precipitation method.« less

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

Hirano, Kazumi; Van Kuppevelt, Toin H.; Nishihara, Shoko, E-mail: shoko@soka.ac.jp

Highlights: ► Fas transcript increases during the transition from the naïve to the primed state. ► 3OST-5 transcript, the HS4C3 epitope synthesis gene, increases during the transition. ► Fas signaling regulates the transition from the naïve to the primed state. ► HS4C3-binding epitope regulates the transition from the naïve to the primed state. ► Fas signaling is regulated by the HS4C3 epitope during the transition. -- Abstract: The characteristics of pluripotent embryonic stem cells of human and mouse are different. The properties of human embryonic stem cells (hESCs) are similar to those of mouse epiblast stem cells (mEpiSCs), which aremore » in a later developmental pluripotency state, the so-called “primed state” compared to mouse embryonic stem cells (mESCs) which are in a naïve state. As a result of the properties of the primed state, hESCs proliferate slowly, cannot survive as single cells, and can only be transfected with genes at low efficiency. Generating hESCs in the naïve state is necessary to overcome these problems and allow their application in regenerative medicine. Therefore, clarifying the mechanism of the transition between the naïve and primed states in pluripotent stem cells is important for the establishment of stable methods of generating naïve state hESCs. However, the signaling pathways which contribute to the transition between the naïve and primed states are still unclear. In this study, we carried out induction from mESCs to mEpiSC-like cells (mEpiSCLCs), and observed an increase in the activation of Fas signaling during the induction. The expression of Fgf5, an epiblast marker, was diminished by inhibition of Fas signaling using the caspase-8 and -3 blocking peptides, IETD and DEVD, respectively. Furthermore, during the induction, we observed increased expression of 3-O sulfated heparan sulfate (HS) structures synthesized by HS 3-O-sulfotransferase (3OST), which are recognized by the HS4C3 antibody (HS4C3-binding epitope). Knockdown of 3OST-5 reduced Fas signaling and the potential for the transition to mEpiSCLCs. This indicates that the HS4C3-binding epitope is necessary for the transition to the primed state. We propose that Fas signaling through the HS4C3-binding epitope contributes to the transition from the naïve state to the primed state.« less

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.

Theoretical studies of solar-pumped lasers

NASA Technical Reports Server (NTRS)

Harries, W. L.

1983-01-01

Metallic vapor lasers of Na2 and Li2 are examined as solar energy converters. The absorbed photons cause transitions to vibrational-rotational levels in an upper electronic state. With broad band absorption the resultant levels can have quantum numbers considerably higher than the upper lasing level. The excited molecule then relaxes to the upper lasing level which is one of the lower vibrational levels in the upper electronic state. The relaxation occurs from collisions, provided the molecule is not quenched into the ground level electronic state. Lasing occurs with a transition to a vibrational level in the lower electronic state. Rough estimates of solar power efficiencies are 1 percent for Na2 and probably a similar figure for Li2. The nondissociative lasers from a family distinct from materials which dissociate to yield an excited atom.

Photosynthetic acclimation: state transitions and adjustment of photosystem stoichiometry--functional relationships between short-term and long-term light quality acclimation in plants.

PubMed

Dietzel, Lars; Bräutigam, Katharina; Pfannschmidt, Thomas

2008-03-01

In dense plant populations, individuals shade each other resulting in a low-light habitat that is enriched in far-red light. This light quality gradient decreases the efficiency of the photosynthetic light reaction as a result of imbalanced excitation of the two photosystems. Plants counteract such conditions by performing acclimation reactions. Two major mechanisms are known to assure efficient photosynthesis: state transitions, which act on a short-term timescale; and a long-term response, which enables the plant to re-adjust photosystem stoichiometry in favour of the rate-limiting photosystem. Both processes start with the perception of the imbalanced photosystem excitation via reduction/oxidation (redox) signals from the photosynthetic electron transport chain. Recent data in Arabidopsis indicate that initialization of the molecular processes in both cases involve the activity of the thylakoid membrane-associated kinase, STN7. Thus, redox-controlled phosphorylation events may not only adjust photosystem antenna structure but may also affect plastid, as well as nuclear, gene expression. Both state transitions and the long-term response have been described mainly in molecular terms, while the physiological relevance concerning plant survival and reproduction has been poorly investigated. Recent studies have shed more light on this topic. Here, we give an overview on the long-term response, its physiological effects, possible mechanisms and its relationship to state transitions as well as to nonphotochemical quenching, another important short-term mechanism that mediates high-light acclimation. Special emphasis is given to the functional roles and potential interactions between the different light acclimation strategies. A working model displays the various responses as an integrated molecular system that helps plants to acclimate to the changing light environment.

Free-end adaptive nudged elastic band method for locating transition states in minimum energy path calculation.

PubMed

Zhang, Jiayong; Zhang, Hongwu; Ye, Hongfei; Zheng, Yonggang

2016-09-07

A free-end adaptive nudged elastic band (FEA-NEB) method is presented for finding transition states on minimum energy paths, where the energy barrier is very narrow compared to the whole paths. The previously proposed free-end nudged elastic band method may suffer from convergence problems because of the kinks arising on the elastic band if the initial elastic band is far from the minimum energy path and weak springs are adopted. We analyze the origin of the formation of kinks and present an improved free-end algorithm to avoid the convergence problem. Moreover, by coupling the improved free-end algorithm and an adaptive strategy, we develop a FEA-NEB method to accurately locate the transition state with the elastic band cut off repeatedly and the density of images near the transition state increased. Several representative numerical examples, including the dislocation nucleation in a penta-twinned nanowire, the twin boundary migration under a shear stress, and the cross-slip of screw dislocation in face-centered cubic metals, are investigated by using the FEA-NEB method. Numerical results demonstrate both the stability and efficiency of the proposed method.

A Three-State System Based on Branched DNA Hybrids.

PubMed

He, Shiliang; Richert, Clemens

2018-03-26

There is a need for materials that respond to chemical or physical stimuli through a change in their structure. While a transition between water-soluble form and solid is not uncommon for DNA-based structures, systems that transition between three different states at room temperature and ambient pressure are rare. Here we report the preparation of branched DNA hybrids with eight oligodeoxycytidylate arms via solution-phase, H-phosphonate-based synthesis. Some hybrids assemble into hydrogels upon lowering the pH, acting as efficient gelators at pH 4-6, but can also transition into a more condensed solid state form upon exposure to divalent cations. Together with the homogeneous solutions that the i-motif-forming compounds give at neutral pH, three-state systems result. Each state has its own color, if chromophores are included in the system. The assembly and gelation properties can be tuned by choosing the chain length of the arms. Their responsive properties make the dC-rich DNA hybrids candidates for smart material applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Computer simulation of magnetic resonance spectra employing homotopy.

PubMed

Gates, K E; Griffin, M; Hanson, G R; Burrage, K

1998-11-01

Multidimensional homotopy provides an efficient method for accurately tracing energy levels and hence transitions in the presence of energy level anticrossings and looping transitions. Herein we describe the application and implementation of homotopy to the analysis of continuous wave electron paramagnetic resonance spectra. The method can also be applied to electron nuclear double resonance, electron spin echo envelope modulation, solid-state nuclear magnetic resonance, and nuclear quadrupole resonance spectra. Copyright 1998 Academic Press.

Relations between the single-pass and double-pass transition probabilities in quantum systems with two and three states

NASA Astrophysics Data System (ADS)

Vitanov, Nikolay V.

2018-05-01

In the experimental determination of the population transfer efficiency between discrete states of a coherently driven quantum system it is often inconvenient to measure the population of the target state. Instead, after the interaction that transfers the population from the initial state to the target state, a second interaction is applied which brings the system back to the initial state, the population of which is easy to measure and normalize. If the transition probability is p in the forward process, then classical intuition suggests that the probability to return to the initial state after the backward process should be p2. However, this classical expectation is generally misleading because it neglects interference effects. This paper presents a rigorous theoretical analysis based on the SU(2) and SU(3) symmetries of the propagators describing the evolution of quantum systems with two and three states, resulting in explicit analytic formulas that link the two-step probabilities to the single-step ones. Explicit examples are given with the popular techniques of rapid adiabatic passage and stimulated Raman adiabatic passage. The present results suggest that quantum-mechanical probabilities degrade faster in repeated processes than classical probabilities. Therefore, the actual single-pass efficiencies in various experiments, calculated from double-pass probabilities, might have been greater than the reported values.

Faithful state transfer between two-level systems via an actively cooled finite-temperature cavity

NASA Astrophysics Data System (ADS)

Sárkány, Lőrinc; Fortágh, József; Petrosyan, David

2018-03-01

We consider state transfer between two qubits—effective two-level systems represented by Rydberg atoms—via a common mode of a microwave cavity at finite temperature. We find that when both qubits have the same coupling strength to the cavity field, at large enough detuning from the cavity mode frequency, quantum interference between the transition paths makes the swap of the excitation between the qubits largely insensitive to the number of thermal photons in the cavity. When, however, the coupling strengths are different, the photon-number-dependent differential Stark shift of the transition frequencies precludes efficient transfer. Nevertheless, using an auxiliary cooling system to continuously extract the cavity photons, we can still achieve a high-fidelity state transfer between the qubits.

Connecticut DOT statewide bus system study : executive summary

DOT National Transportation Integrated Search

2000-07-01

The Connecticut Statewide Bus System Study has been undertaken to ensure that bus transit in Connecticut serves continuing needs in the most efficient manner possible. The Study has taken a comprehensive look at the state's twenty urban and rural tra...

Partial information, market efficiency, and anomalous continuous phase transition

NASA Astrophysics Data System (ADS)

Yang, Guang; Zheng, Wenzhi; Huang, Jiping

2014-04-01

It is a common belief in economics and social science that if there is more information available for agents to gather in a human system, the system can become more efficient. The belief can be easily understood according to the well-known efficient market hypothesis. In this work, we attempt to challenge this belief by investigating a complex adaptive system, which is modeled by a market-directed resource-allocation game with a directed random network. We conduct a series of controlled human experiments in the laboratory to show the reliability of the model design. As a result, we find that even under a small information concentration, the system can still almost reach the optimal (balanced) state. Furthermore, the ensemble average of the system’s fluctuation level goes through a continuous phase transition. This behavior means that in the second phase if too much information is shared among agents, the system’s stability will be harmed instead, which differs from the belief mentioned above. Also, at the transition point, the ensemble fluctuations of the fluctuation level remain at a low value. This phenomenon is in contrast to the textbook knowledge about continuous phase transitions in traditional physical systems, namely, fluctuations will rise abnormally around a transition point since the correlation length becomes infinite. Thus, this work is of potential value to a variety of fields, such as physics, economics, complexity science, and artificial intelligence.

Enhanced sampling simulation analysis of the structure of lignin in the THF–water miscibility gap

DOE PAGES

Smith, Micholas Dean; Petridis, Loukas; Cheng, Xiaolin; ...

2016-01-26

Using temperature replica-exchange molecular dynamics, we characterize a globule-to-coil transition for a softwood-like lignin biopolymer in a tetrahydrofuran (THF)-water cosolvent system at temperatures at which the cosolvent undergoes a de-mixing transition. The lignin is found to be in a coil state, similar to that in the high-temperature miscible region. Analysis of the transition kinetics indicates that THF acts in a surfactant-like fashion. In conclusion, the present study thus suggests that THF-water based pretreatments may efficiently remove lignin from biomass even at relatively low (non-water boiling) temperatures.

Energy-Looping Nanoparticles: Harnessing Excited-State Absorption for Deep-Tissue Imaging.

PubMed

Levy, Elizabeth S; Tajon, Cheryl A; Bischof, Thomas S; Iafrati, Jillian; Fernandez-Bravo, Angel; Garfield, David J; Chamanzar, Maysamreza; Maharbiz, Michel M; Sohal, Vikaas S; Schuck, P James; Cohen, Bruce E; Chan, Emory M

2016-09-27

Near infrared (NIR) microscopy enables noninvasive imaging in tissue, particularly in the NIR-II spectral range (1000-1400 nm) where attenuation due to tissue scattering and absorption is minimized. Lanthanide-doped upconverting nanocrystals are promising deep-tissue imaging probes due to their photostable emission in the visible and NIR, but these materials are not efficiently excited at NIR-II wavelengths due to the dearth of lanthanide ground-state absorption transitions in this window. Here, we develop a class of lanthanide-doped imaging probes that harness an energy-looping mechanism that facilitates excitation at NIR-II wavelengths, such as 1064 nm, that are resonant with excited-state absorption transitions but not ground-state absorption. Using computational methods and combinatorial screening, we have identified Tm(3+)-doped NaYF4 nanoparticles as efficient looping systems that emit at 800 nm under continuous-wave excitation at 1064 nm. Using this benign excitation with standard confocal microscopy, energy-looping nanoparticles (ELNPs) are imaged in cultured mammalian cells and through brain tissue without autofluorescence. The 1 mm imaging depths and 2 μm feature sizes are comparable to those demonstrated by state-of-the-art multiphoton techniques, illustrating that ELNPs are a promising class of NIR probes for high-fidelity visualization in cells and tissue.

Optical Feshbach resonances and ground-state-molecule production in the RbHg system

NASA Astrophysics Data System (ADS)

Borkowski, Mateusz; Muñoz Rodriguez, Rodolfo; Kosicki, Maciej B.; Ciuryło, Roman; Żuchowski, Piotr S.

2017-12-01

We present the prospects for photoassociation, optical control of interspecies scattering lengths, and, finally, the production of ultracold absolute ground-state molecules in the Rb+Hg system. We use the state-of-the-art ab initio methods for the calculations of ground- [CCSD(T)] and excited-state (EOM-CCSD) potential curves. The RbHg system, thanks to the wide range of stable Hg bosonic isotopes, offers possibilities for mass tuning of ground-state interactions. The optical lengths describing the strengths of optical Feshbach resonances near the Rb transitions are favorable even at large laser detunings. Ground-state RbHg molecules can be produced with efficiencies ranging from about 20% for deeply bound to at least 50% for weakly bound states close to the dissociation limit. Finally, electronic transitions with favorable Franck-Condon factors can be found for the purposes of a STIRAP transfer of the weakly bound RbHg molecules to the absolute ground state using commercially available lasers.

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.

Kinetic model of stimulated emission created by resonance pumping of aluminum laser-induced plasma

NASA Astrophysics Data System (ADS)

Gornushkin, I. B.; Kazakov, A. Ya.

2017-06-01

Stimulated emission observed experimentally in an aluminum laser induced plasma is modeled via a kinetic approach. The simulated emission at several cascade transitions is created by a pump laser guided through the plasma at several microseconds after its creation and tuned in resonance with the strong 3s23p-3s24s transition at 266 nm. A two-dimensional space-time collisional radiative plasma model explains the creation of the population inversion and lasing at wavelengths of 2100 n m and 396.1 nm. The population inversion for lasing at 2100 n m is created by depopulation of the ground 3s23p state and population of the 3s25s state via the absorption of the resonant radiation at 266 nm. The population inversion for lasing at 396.1 nm occurs during the laser pulse via the decay of the population of the pumped 3s25s state to the excited 3s24s state via cascade transitions driven optically and by collisions. In particular, efficient are the mixing transitions between neighboring states separated by small gaps on the order of k T at plasma temperatures of 5000-10 000 K. The model predicts that the population inversion and corresponding gain may reach high values even at very moderate pump energy of several μJ per pulse. The efficiency of lasing at 2100 n m and 396.1 nm is estimated to be ˜3% and 0.05%, correspondingly with respect to the pump laser intensity. The gain for lasing at 396.1 nm can reach as high as ˜40 cm-1. The polarization effect that the pump radiation at 266 nm imposes on the stimulated emission at 396.1 nm is discussed. The calculated results are favorably compared to experimental data.

Augmenting the efficacy of anti-cocaine catalytic antibodies through chimeric hapten design and combinatorial vaccination.

PubMed

Wenthur, Cody J; Cai, Xiaoqing; Ellis, Beverly A; Janda, Kim D

2017-08-15

Given the need for further improvements in anti-cocaine vaccination strategies, a chimeric hapten (GNET) was developed that combines chemically-stable structural features from steady-state haptens with the hydrolytic functionality present in transition-state mimetic haptens. Additionally, as a further investigation into the generation of an improved bifunctional antibody pool, sequential vaccination with steady-state and transition-state mimetic haptens was undertaken. While GNET induced the formation of catalytically-active antibodies, it did not improve overall behavioral efficacy. In contrast, the resulting pool of antibodies from GNE/GNT co-administration demonstrated intermediate efficacy as compared to antibodies developed from either hapten alone. Overall, improved antibody catalytic efficiency appears necessary to achieve the synergistic benefits of combining cocaine hydrolysis with peripheral sequestration. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tracking the deployment of the integrated metropolitan intelligent transportation systems infrastructure in The USA : FY99 results

DOT National Transportation Integrated Search

1998-09-16

One of the new requirements of the Intermodal Surface Transportation Efficiency Act of 1991 is the requirement that State Departments of Transportation, Metropolitan Planning Organizations, and transit operators conduct a major investment study (MIS)...

How can we maximize efficiency and increase person occupancy at overcrowded park and rides?

DOT National Transportation Integrated Search

2014-06-01

This study was conducted in cooperation with the U.S. Department of Transportation and Federal Highway Administration. The purpose of this project was to provide the Washington State Department of Transportation (WSDOT), King County Metro Transit, an...

Insight into the Structural and Biological Relevance of the T/R Transition of the N-Terminus of the B-Chain in Human Insulin

PubMed Central

2014-01-01

The N-terminus of the B-chain of insulin may adopt two alternative conformations designated as the T- and R-states. Despite the recent structural insight into insulin–insulin receptor (IR) complexes, the physiological relevance of the T/R transition is still unclear. Hence, this study focused on the rational design, synthesis, and characterization of human insulin analogues structurally locked in expected R- or T-states. Sites B3, B5, and B8, capable of affecting the conformation of the N-terminus of the B-chain, were subjects of rational substitutions with amino acids with specific allowed and disallowed dihedral φ and ψ main-chain angles. α-Aminoisobutyric acid was systematically incorporated into positions B3, B5, and B8 for stabilization of the R-state, and N-methylalanine and d-proline amino acids were introduced at position B8 for stabilization of the T-state. IR affinities of the analogues were compared and correlated with their T/R transition ability and analyzed against their crystal and nuclear magnetic resonance structures. Our data revealed that (i) the T-like state is indeed important for the folding efficiency of (pro)insulin, (ii) the R-state is most probably incompatible with an active form of insulin, (iii) the R-state cannot be induced or stabilized by a single substitution at a specific site, and (iv) the B1–B8 segment is capable of folding into a variety of low-affinity T-like states. Therefore, we conclude that the active conformation of the N-terminus of the B-chain must be different from the “classical” T-state and that a substantial flexibility of the B1–B8 segment, where GlyB8 plays a key role, is a crucial prerequisite for an efficient insulin–IR interaction. PMID:24819248

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.

Memory-efficient RNA energy landscape exploration

PubMed Central

Mann, Martin; Kucharík, Marcel; Flamm, Christoph; Wolfinger, Michael T.

2014-01-01

Motivation: Energy landscapes provide a valuable means for studying the folding dynamics of short RNA molecules in detail by modeling all possible structures and their transitions. Higher abstraction levels based on a macro-state decomposition of the landscape enable the study of larger systems; however, they are still restricted by huge memory requirements of exact approaches. Results: We present a highly parallelizable local enumeration scheme that enables the computation of exact macro-state transition models with highly reduced memory requirements. The approach is evaluated on RNA secondary structure landscapes using a gradient basin definition for macro-states. Furthermore, we demonstrate the need for exact transition models by comparing two barrier-based approaches, and perform a detailed investigation of gradient basins in RNA energy landscapes. Availability and implementation: Source code is part of the C++ Energy Landscape Library available at http://www.bioinf.uni-freiburg.de/Software/. Contact: mmann@informatik.uni-freiburg.de Supplementary information: Supplementary data are available at Bioinformatics online. PMID:24833804

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.

Transition-metal doped sulfide, selenide, and telluride laser crystal and lasers

DOEpatents

Krupke, W.F.; Page, R.H.; DeLoach, L.D.; Payne, S.A.

1996-07-30

A new class of solid state laser crystals and lasers are formed of transition metal doped sulfide, selenide, and telluride host crystals which have four fold coordinated substitutional sites. The host crystals include II-VI compounds. The host crystal is doped with a transition metal laser ion, e.g., chromium, cobalt or iron. In particular, Cr{sup 2+}-doped ZnS and ZnSe generate laser action near 2.3 {micro}m. Oxide, chloride, fluoride, bromide and iodide crystals with similar structures can also be used. Important aspects of these laser materials are the tetrahedral site symmetry of the host crystal, low excited state absorption losses and high luminescence efficiency, and the d{sup 4} and d{sup 6} electronic configurations of the transition metal ions. The same materials are also useful as saturable absorbers for passive Q-switching applications. The laser materials can be used as gain media in amplifiers and oscillators; these gain media can be incorporated into waveguides and semiconductor lasers. 18 figs.

Transition-metal doped sulfide, selenide, and telluride laser crystal and lasers

DOEpatents

Krupke, William F.; Page, Ralph H.; DeLoach, Laura D.; Payne, Stephen A.

1996-01-01

A new class of solid state laser crystals and lasers are formed of transition metal doped sulfide, selenide, and telluride host crystals which have four fold coordinated substitutional sites. The host crystals include II-VI compounds. The host crystal is doped with a transition metal laser ion, e.g., chromium, cobalt or iron. In particular, Cr.sup.2+ -doped ZnS and ZnSe generate laser action near 2.3 .mu.m. Oxide, chloride, fluoride, bromide and iodide crystals with similar structures can also be used. Important aspects of these laser materials are the tetrahedral site symmetry of the host crystal, low excited state absorption losses and high luminescence efficiency, and the d.sup.4 and d.sup.6 electronic configurations of the transition metal ions. The same materials are also useful as saturable absorbers for passive Q-switching applications. The laser materials can be used as gain media in amplifiers and oscillators; these gain media can be incorporated into waveguides and semiconductor lasers.

Molecular Remodeling of Photosystem II during State Transitions in Chlamydomonas reinhardtii[W

PubMed Central

Iwai, Masakazu; Takahashi, Yuichiro; Minagawa, Jun

2008-01-01

State transitions, or the redistribution of light-harvesting complex II (LHCII) proteins between photosystem I (PSI) and photosystem II (PSII), balance the light-harvesting capacity of the two photosystems to optimize the efficiency of photosynthesis. Studies on the migration of LHCII proteins have focused primarily on their reassociation with PSI, but the molecular details on their dissociation from PSII have not been clear. Here, we compare the polypeptide composition, supramolecular organization, and phosphorylation of PSII complexes under PSI- and PSII-favoring conditions (State 1 and State 2, respectively). Three PSII fractions, a PSII core complex, a PSII supercomplex, and a multimer of PSII supercomplex or PSII megacomplex, were obtained from a transformant of the green alga Chlamydomonas reinhardtii carrying a His-tagged CP47. Gel filtration and single particles on electron micrographs showed that the megacomplex was predominant in State 1, whereas the core complex was predominant in State 2, indicating that LHCIIs are dissociated from PSII upon state transition. Moreover, in State 2, strongly phosphorylated LHCII type I was found in the supercomplex but not in the megacomplex. Phosphorylated minor LHCIIs (CP26 and CP29) were found only in the unbound form. The PSII subunits were most phosphorylated in the core complex. Based on these observations, we propose a model for PSII remodeling during state transitions, which involves division of the megacomplex into supercomplexes, triggered by phosphorylation of LHCII type I, followed by LHCII undocking from the supercomplex, triggered by phosphorylation of minor LHCIIs and PSII core subunits. PMID:18757554

Forecasting client transitions in British Columbia's Long-Term Care Program.

PubMed Central

Lane, D; Uyeno, D; Stark, A; Gutman, G; McCashin, B

1987-01-01

This article presents a model for the annual transitions of clients through various home and facility placements in a long-term care program. The model, an application of Markov chain analysis, is developed, tested, and applied to over 9,000 clients (N = 9,483) in British Columbia's Long Term Care Program (LTC) over the period 1978-1983. Results show that the model gives accurate forecasts of the progress of groups of clients from state to state in the long-term care system from time of admission until eventual death. Statistical methods are used to test the modeling hypothesis that clients' year-over-year transitions occur in constant proportions from state to state within the long-term care system. Tests are carried out by examining actual year-over-year transitions of each year's new admission cohort (1978-1983). Various subsets of the available data are analyzed and, after accounting for clear differences among annual cohorts, the most acceptable model of the actual client transition data occurred when clients were separated into male and female groups, i.e., the transition behavior of each group is describable by a different Markov model. To validate the model, we develop model estimates for the numbers of existing clients in each state of the long-term care system for the period (1981-1983) for which actual data are available. When these estimates are compared with the actual data, total weighted absolute deviations do not exceed 10 percent of actuals. Finally, we use the properties of the Markov chain probability transition matrix and simulation methods to develop three-year forecasts with prediction intervals for the distribution of the existing total clients into each state of the system. The tests, forecasts, and Markov model supplemental information are contained in a mechanized procedure suitable for a microcomputer. The procedure provides a powerful, efficient tool for decision makers planning facilities and services in response to the needs of long-term care clients. PMID:3121537

Luminescence upconversion under hydrostatic pressure in the 3d-metal systems Ti2+:NaCl and Ni2+:CsCdCl3

NASA Astrophysics Data System (ADS)

Wenger, Oliver S.; Salley, G. Mackay; Valiente, Rafael; Güdel, Hans U.

2002-06-01

We present a study of upconversion materials and processes under external hydrostatic pressure. The near-infrared to visible photon upconversion properties of Ti2+-doped NaCl and Ni2+-doped CsCdCl3 at 15 K are studied as a function of external hydrostatic pressure. It is found that in Ti2+:NaCl pressure can be used to switch on an efficient upconversion mechanism, which is inactive at ambient pressure, leading to an order-of-magnitude enhancement of the overall upconversion efficiency of this material. For Ni2+:CsCdCl3 it is demonstrated that upconversion luminescence excitation spectroscopy can be used to study the pressure dependence of excited state absorption transitions. The results demonstrate the ability to tune upconversion properties by altering the local crystal field of active ions, in addition to probing the pressure dependence of excited state absorption transitions via upconversion spectroscopy.

New Diamond Color Center for Quantum Communication

NASA Astrophysics Data System (ADS)

Huang, Ding; Rose, Brendon; Tyryshkin, Alexei; Sangtawesin, Sorawis; Srinivasan, Srikanth; Twitchen, Daniel; Markham, Matthew; Edmonds, Andrew; Gali, Adam; Stacey, Alastair; Wang, Wuyi; D'Haenens-Johansson, Ulrika; Zaitsev, Alexandre; Lyon, Stephen; de Leon, Nathalie

2017-04-01

Color centers in diamond are attractive for quantum communication applications because of their long electron spin coherence times and efficient optical transitions. Previous demonstrations of color centers as solid-state spin qubits were primarily focused on centers that exhibit either long coherence times or highly efficient optical interfaces. Recently, we developed a method to stabilize the neutral charge state of silicon-vacancy center in diamond (SiV0) with high conversion efficiency. We observe spin relaxation times exceeding 1 minute and spin coherence times of 1 ms for SiV0 centers. Additionally, the SiV0 center also has > 90 % of its emission into its zero-phonon line and a narrow inhomogeneous optical linewidth. The combination of a long spin coherence time and efficient optical interface make the SiV0 center a promising candidate for applications in long distance quantum communication.

Promoting Singlet/triplet Exciton Transformation in Organic Optoelectronic Molecules: Role of Excited State Transition Configuration.

PubMed

Chen, Runfeng; Tang, Yuting; Wan, Yifang; Chen, Ting; Zheng, Chao; Qi, Yuanyuan; Cheng, Yuanfang; Huang, Wei

2017-07-24

Exciton transformation, a non-radiative process in changing the spin multiplicity of an exciton usually between singlet and triplet forms, has received much attention recently due to its crucial effects in manipulating optoelectronic properties for various applications. However, current understanding of exciton transformation mechanism does not extend far beyond a thermal equilibrium of two states with different multiplicity and it is a significant challenge to probe what exactly control the transformation between the highly active excited states. Here, based on the recent developments of three types of purely organic molecules capable of efficient spin-flipping, we perform ab initio structure/energy optimization and similarity/overlap extent analysis to theoretically explore the critical factors in controlling the transformation process of the excited states. The results suggest that the states having close energy levels and similar exciton characteristics with same transition configurations and high heteroatom participation are prone to facilitating exciton transformation. A basic guideline towards the molecular design of purely organic materials with facile exciton transformation ability is also proposed. Our discovery highlights systematically the critical importance of vertical transition configuration of excited states in promoting the singlet/triplet exciton transformation, making a key step forward in excited state tuning of purely organic optoelectronic materials.

Distinct properties of the triplet pair state from singlet fission

DOE PAGES

Trinh, M. Tuan; Pinkard, Andrew; Pun, Andrew B.; ...

2017-07-14

Singlet fission, the conversion of a singlet exciton (S 1) to two triplets (2 × T 1), may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. This process is believed to involve the correlated triplet pair state 1(TT). Despite extensive research, the nature of the 1(TT) state and its spectroscopic signature remain actively debated. We use an end-connected pentacene dimer (BP0) as a model system and show evidence for a tightly bound 1(TT) state. It is characterized in the near-infrared (IR) region (~1.0 eV) by a distinct excited-state absorption (ESA) spectral feature, which closely resembles that of themore » S 1 state; both show vibronic progressions of the aromatic ring breathing mode. We assign these near-IR spectra to 1(TT)→S n and S 1→S n' transitions; S n and S n' likely come from the antisymmetric and symmetric linear combinations, respectively, of the S 2 state localized on each pentacene unit in the dimer molecule. The 1(TT)→S n transition is an indicator of the intertriplet electronic coupling strength, because inserting a phenylene spacer or twisting the dihedral angle between the two pentacene chromophores decreases the intertriplet electronic coupling and diminishes this ESA peak. In addition to spectroscopic signature, the tightly bound 1(TT) state also shows chemical reactivity that is distinctively different from that of an individual T 1 state. Using an electron-accepting iron oxide molecular cluster [Fe 8O 4] linked to the pentacene or pentacene dimer (BP0), we show that electron transfer to the cluster occurs efficiently from an individual T 1 in pentacene but not from the tightly bound 1(TT) state. Thus, reducing intertriplet electronic coupling in 1(TT) via molecular design might be necessary for the efficient harvesting of triplets from intramolecular singlet fission.« less

Distinct properties of the triplet pair state from singlet fission.

PubMed

Trinh, M Tuan; Pinkard, Andrew; Pun, Andrew B; Sanders, Samuel N; Kumarasamy, Elango; Sfeir, Matthew Y; Campos, Luis M; Roy, Xavier; Zhu, X-Y

2017-07-01

Singlet fission, the conversion of a singlet exciton (S 1 ) to two triplets (2 × T 1 ), may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. This process is believed to involve the correlated triplet pair state 1 (TT). Despite extensive research, the nature of the 1 (TT) state and its spectroscopic signature remain actively debated. We use an end-connected pentacene dimer (BP0) as a model system and show evidence for a tightly bound 1 (TT) state. It is characterized in the near-infrared (IR) region (~1.0 eV) by a distinct excited-state absorption (ESA) spectral feature, which closely resembles that of the S 1 state; both show vibronic progressions of the aromatic ring breathing mode. We assign these near-IR spectra to 1 (TT)→S n and S 1 →S n' transitions; S n and S n' likely come from the antisymmetric and symmetric linear combinations, respectively, of the S 2 state localized on each pentacene unit in the dimer molecule. The 1 (TT)→S n transition is an indicator of the intertriplet electronic coupling strength, because inserting a phenylene spacer or twisting the dihedral angle between the two pentacene chromophores decreases the intertriplet electronic coupling and diminishes this ESA peak. In addition to spectroscopic signature, the tightly bound 1 (TT) state also shows chemical reactivity that is distinctively different from that of an individual T 1 state. Using an electron-accepting iron oxide molecular cluster [Fe 8 O 4 ] linked to the pentacene or pentacene dimer (BP0), we show that electron transfer to the cluster occurs efficiently from an individual T 1 in pentacene but not from the tightly bound 1 (TT) state. Thus, reducing intertriplet electronic coupling in 1 (TT) via molecular design might be necessary for the efficient harvesting of triplets from intramolecular singlet fission.

Distinct properties of the triplet pair state from singlet fission

PubMed Central

Trinh, M. Tuan; Pinkard, Andrew; Pun, Andrew B.; Sanders, Samuel N.; Kumarasamy, Elango; Sfeir, Matthew Y.; Campos, Luis M.; Roy, Xavier; Zhu, X.-Y.

2017-01-01

Singlet fission, the conversion of a singlet exciton (S1) to two triplets (2 × T1), may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. This process is believed to involve the correlated triplet pair state 1(TT). Despite extensive research, the nature of the 1(TT) state and its spectroscopic signature remain actively debated. We use an end-connected pentacene dimer (BP0) as a model system and show evidence for a tightly bound 1(TT) state. It is characterized in the near-infrared (IR) region (~1.0 eV) by a distinct excited-state absorption (ESA) spectral feature, which closely resembles that of the S1 state; both show vibronic progressions of the aromatic ring breathing mode. We assign these near-IR spectra to 1(TT)→Sn and S1→Sn′ transitions; Sn and Sn′ likely come from the antisymmetric and symmetric linear combinations, respectively, of the S2 state localized on each pentacene unit in the dimer molecule. The 1(TT)→Sn transition is an indicator of the intertriplet electronic coupling strength, because inserting a phenylene spacer or twisting the dihedral angle between the two pentacene chromophores decreases the intertriplet electronic coupling and diminishes this ESA peak. In addition to spectroscopic signature, the tightly bound 1(TT) state also shows chemical reactivity that is distinctively different from that of an individual T1 state. Using an electron-accepting iron oxide molecular cluster [Fe8O4] linked to the pentacene or pentacene dimer (BP0), we show that electron transfer to the cluster occurs efficiently from an individual T1 in pentacene but not from the tightly bound 1(TT) state. Thus, reducing intertriplet electronic coupling in 1(TT) via molecular design might be necessary for the efficient harvesting of triplets from intramolecular singlet fission. PMID:28740866

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.

A multi-band, multi-level, multi-electron model for efficient FDTD simulations of electromagnetic interactions with semiconductor quantum wells

NASA Astrophysics Data System (ADS)

Ravi, Koustuban; Wang, Qian; Ho, Seng-Tiong

2015-08-01

We report a new computational model for simulations of electromagnetic interactions with semiconductor quantum well(s) (SQW) in complex electromagnetic geometries using the finite-difference time-domain method. The presented model is based on an approach of spanning a large number of electron transverse momentum states in each SQW sub-band (multi-band) with a small number of discrete multi-electron states (multi-level, multi-electron). This enables accurate and efficient two-dimensional (2-D) and three-dimensional (3-D) simulations of nanophotonic devices with SQW active media. The model includes the following features: (1) Optically induced interband transitions between various SQW conduction and heavy-hole or light-hole sub-bands are considered. (2) Novel intra sub-band and inter sub-band transition terms are derived to thermalize the electron and hole occupational distributions to the correct Fermi-Dirac distributions. (3) The terms in (2) result in an explicit update scheme which circumvents numerically cumbersome iterative procedures. This significantly augments computational efficiency. (4) Explicit update terms to account for carrier leakage to unconfined states are derived, which thermalize the bulk and SQW populations to a common quasi-equilibrium Fermi-Dirac distribution. (5) Auger recombination and intervalence band absorption are included. The model is validated by comparisons to analytic band-filling calculations, simulations of SQW optical gain spectra, and photonic crystal lasers.

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.

Transition between Functional Regimes in an Integrate-And-Fire Network Model of the Thalamus

PubMed Central

Barardi, Alessandro; Mazzoni, Alberto

2016-01-01

The thalamus is a key brain element in the processing of sensory information. During the sleep and awake states, this brain area is characterized by the presence of two distinct dynamical regimes: in the sleep state activity is dominated by spindle oscillations (7 − 15 Hz) weakly affected by external stimuli, while in the awake state the activity is primarily driven by external stimuli. Here we develop a simple and computationally efficient model of the thalamus that exhibits two dynamical regimes with different information-processing capabilities, and study the transition between them. The network model includes glutamatergic thalamocortical (TC) relay neurons and GABAergic reticular (RE) neurons described by adaptive integrate-and-fire models in which spikes are induced by either depolarization or hyperpolarization rebound. We found a range of connectivity conditions under which the thalamic network composed by these neurons displays the two aforementioned dynamical regimes. Our results show that TC-RE loops generate spindle-like oscillations and that a minimum level of clustering (i.e. local connectivity density) in the RE-RE connections is necessary for the coexistence of the two regimes. We also observe that the transition between the two regimes occurs when the external excitatory input on TC neurons (mimicking sensory stimulation) is large enough to cause a significant fraction of them to switch from hyperpolarization-rebound-driven firing to depolarization-driven firing. Overall, our model gives a novel and clear description of the role that the two types of neurons and their connectivity play in the dynamical regimes observed in the thalamus, and in the transition between them. These results pave the way for the development of efficient models of the transmission of sensory information from periphery to cortex. PMID:27598260

Upconversion excitations in Pr3+-doped BaY2F8 crystal

NASA Astrophysics Data System (ADS)

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

2011-09-01

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

Lifetime enhancement for multiphoton absorption in intermediate band solar cells

NASA Astrophysics Data System (ADS)

Bezerra, Anibal T.; Studart, Nelson

2017-08-01

A semiconductor structure consisting of two coupled quantum wells embedded into the intrinsic region of a p-i-n junction is proposed as an intermediate band solar cell with a photon ratchet state, which would lead to increasing the cell efficiency. The conduction subband of the right-hand side quantum well works as the intermediated band, whereas the excited conduction subband of the left-hand side quantum well operates as the ratchet state. The photoelectrons in the intermediate band are scattered through the thin wells barrier and accumulated into the ratchet subband. A rate equation model for describing the charge transport properties is presented. The efficiency of the current generation is analyzed by studying the occupation of the wells subbands, taking into account the charge dynamic behavior provided by the electrical contacts connected to the cell. The current generation efficiency depends essentially from the relations between the generation, recombination rates and the scattering rate to the ratchet state. The inclusion of the ratchet states led to both an increase and a decrease in the cell current depending on the transition rates. This suggests that the coupling between the intermediate band and the ratchet state is a key point in developing an efficient solar cell.

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

Trinh, M. Tuan; Pinkard, Andrew; Pun, Andrew B.

Singlet fission, the conversion of a singlet exciton (S 1) to two triplets (2 × T 1), may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. This process is believed to involve the correlated triplet pair state 1(TT). Despite extensive research, the nature of the 1(TT) state and its spectroscopic signature remain actively debated. We use an end-connected pentacene dimer (BP0) as a model system and show evidence for a tightly bound 1(TT) state. It is characterized in the near-infrared (IR) region (~1.0 eV) by a distinct excited-state absorption (ESA) spectral feature, which closely resembles that of themore » S 1 state; both show vibronic progressions of the aromatic ring breathing mode. We assign these near-IR spectra to 1(TT)→S n and S 1→S n' transitions; S n and S n' likely come from the antisymmetric and symmetric linear combinations, respectively, of the S 2 state localized on each pentacene unit in the dimer molecule. The 1(TT)→S n transition is an indicator of the intertriplet electronic coupling strength, because inserting a phenylene spacer or twisting the dihedral angle between the two pentacene chromophores decreases the intertriplet electronic coupling and diminishes this ESA peak. In addition to spectroscopic signature, the tightly bound 1(TT) state also shows chemical reactivity that is distinctively different from that of an individual T 1 state. Using an electron-accepting iron oxide molecular cluster [Fe 8O 4] linked to the pentacene or pentacene dimer (BP0), we show that electron transfer to the cluster occurs efficiently from an individual T 1 in pentacene but not from the tightly bound 1(TT) state. Thus, reducing intertriplet electronic coupling in 1(TT) via molecular design might be necessary for the efficient harvesting of triplets from intramolecular singlet fission.« less

First-principles engineering of charged defects for two-dimensional quantum technologies

NASA Astrophysics Data System (ADS)

Wu, Feng; Galatas, Andrew; Sundararaman, Ravishankar; Rocca, Dario; Ping, Yuan

2017-12-01

Charged defects in two-dimensional (2D) materials have emerging applications in quantum technologies such as quantum emitters and quantum computation. The advancement of these technologies requires a rational design of ideal defect centers, demanding reliable computation methods for the quantitatively accurate prediction of defect properties. We present an accurate, parameter-free, and efficient procedure to evaluate the quasiparticle defect states and thermodynamic charge transition levels of defects in 2D materials. Importantly, we solve critical issues that stem from the strongly anisotropic screening in 2D materials, that have so far precluded the accurate prediction of charge transition levels in these materials. Using this procedure, we investigate various defects in monolayer hexagonal boron nitride (h -BN ) for their charge transition levels, stable spin states, and optical excitations. We identify CBVN (nitrogen vacancy adjacent to carbon substitution of boron) to be the most promising defect candidate for scalable quantum bit and emitter applications.

Efficient Learning of Continuous-Time Hidden Markov Models for Disease Progression

PubMed Central

Liu, Yu-Ying; Li, Shuang; Li, Fuxin; Song, Le; Rehg, James M.

2016-01-01

The Continuous-Time Hidden Markov Model (CT-HMM) is an attractive approach to modeling disease progression due to its ability to describe noisy observations arriving irregularly in time. However, the lack of an efficient parameter learning algorithm for CT-HMM restricts its use to very small models or requires unrealistic constraints on the state transitions. In this paper, we present the first complete characterization of efficient EM-based learning methods for CT-HMM models. We demonstrate that the learning problem consists of two challenges: the estimation of posterior state probabilities and the computation of end-state conditioned statistics. We solve the first challenge by reformulating the estimation problem in terms of an equivalent discrete time-inhomogeneous hidden Markov model. The second challenge is addressed by adapting three approaches from the continuous time Markov chain literature to the CT-HMM domain. We demonstrate the use of CT-HMMs with more than 100 states to visualize and predict disease progression using a glaucoma dataset and an Alzheimer’s disease dataset. PMID:27019571

Can quantum coherent solar cells break detailed balance?

NASA Astrophysics Data System (ADS)

Kirk, Alexander P.

2015-07-01

Carefully engineered coherent quantum states have been proposed as a design attribute that is hypothesized to enable solar photovoltaic cells to break the detailed balance (or radiative) limit of power conversion efficiency by possibly causing radiative recombination to be suppressed. However, in full compliance with the principles of statistical mechanics and the laws of thermodynamics, specially prepared coherent quantum states do not allow a solar photovoltaic cell—a quantum threshold energy conversion device—to exceed the detailed balance limit of power conversion efficiency. At the condition given by steady-state open circuit operation with zero nonradiative recombination, the photon absorption rate (or carrier photogeneration rate) must balance the photon emission rate (or carrier radiative recombination rate) thus ensuring that detailed balance prevails. Quantum state transitions, entropy-generating hot carrier relaxation, and photon absorption and emission rate balancing are employed holistically and self-consistently along with calculations of current density, voltage, and power conversion efficiency to explain why detailed balance may not be violated in solar photovoltaic cells.

Efficient cooling of quantized vibrations using a four-level configuration

NASA Astrophysics Data System (ADS)

Yan, Lei-Lei; Zhang, Jian-Qi; Zhang, Shuo; Feng, Mang

2016-12-01

Cooling vibrational degrees of freedom down to ground states is essential to observation of quantum properties of systems with mechanical vibration. We propose two cooling schemes employing four internal levels of the systems, which achieve the ground-state cooling in an efficient fashion by completely deleting the carrier and first-order blue-sideband transitions. The schemes, based on quantum interference and Stark-shift gates, are robust to fluctuations of laser intensity and frequency. The feasibility of the schemes is justified using current laboratory technology. In practice, our proposal readily applies to a nanodiamond nitrogen-vacancy center levitated in an optical trap or attached to a cantilever.

Coherence time of over a second in a telecom-compatible quantum memory storage material

NASA Astrophysics Data System (ADS)

Rančić, Miloš; Hedges, Morgan P.; Ahlefeldt, Rose L.; Sellars, Matthew J.

2018-01-01

Quantum memories for light will be essential elements in future long-range quantum communication networks. These memories operate by reversibly mapping the quantum state of light onto the quantum transitions of a material system. For networks, the quantum coherence times of these transitions must be long compared to the network transmission times, approximately 100 ms for a global communication network. Due to a lack of a suitable storage material, a quantum memory that operates in the 1,550 nm optical fibre communication band with a storage time greater than 1 μs has not been demonstrated. Here we describe the spin dynamics of 167Er3+: Y2SiO5 in a high magnetic field and demonstrate that this material has the characteristics for a practical quantum memory in the 1,550 nm communication band. We observe a hyperfine coherence time of 1.3 s. We also demonstrate efficient spin pumping of the entire ensemble into a single hyperfine state, a requirement for broadband spin-wave storage. With an absorption of 70 dB cm-1 at 1,538 nm and Λ transitions enabling spin-wave storage, this material is the first candidate identified for an efficient, broadband quantum memory at telecommunication wavelengths.

Precision is essential for efficient catalysis in an evolved Kemp eliminase.

PubMed

Blomberg, Rebecca; Kries, Hajo; Pinkas, Daniel M; Mittl, Peer R E; Grütter, Markus G; Privett, Heidi K; Mayo, Stephen L; Hilvert, Donald

2013-11-21

Linus Pauling established the conceptual framework for understanding and mimicking enzymes more than six decades ago. The notion that enzymes selectively stabilize the rate-limiting transition state of the catalysed reaction relative to the bound ground state reduces the problem of design to one of molecular recognition. Nevertheless, past attempts to capitalize on this idea, for example by using transition state analogues to elicit antibodies with catalytic activities, have generally failed to deliver true enzymatic rates. The advent of computational design approaches, combined with directed evolution, has provided an opportunity to revisit this problem. Starting from a computationally designed catalyst for the Kemp elimination--a well-studied model system for proton transfer from carbon--we show that an artificial enzyme can be evolved that accelerates an elementary chemical reaction 6 × 10(8)-fold, approaching the exceptional efficiency of highly optimized natural enzymes such as triosephosphate isomerase. A 1.09 Å resolution crystal structure of the evolved enzyme indicates that familiar catalytic strategies such as shape complementarity and precisely placed catalytic groups can be successfully harnessed to afford such high rate accelerations, making us optimistic about the prospects of designing more sophisticated catalysts.

QM/MM simulations identify the determinants of catalytic activity differences between type II dehydroquinase enzymes.

PubMed

Lence, Emilio; van der Kamp, Marc W; González-Bello, Concepción; Mulholland, Adrian J

2018-05-16

Type II dehydroquinase enzymes (DHQ2), recognized targets for antibiotic drug discovery, show significantly different activities dependent on the species: DHQ2 from Mycobacterium tuberculosis (MtDHQ2) and Helicobacter pylori (HpDHQ2) show a 50-fold difference in catalytic efficiency. Revealing the determinants of this activity difference is important for our understanding of biological catalysis and further offers the potential to contribute to tailoring specificity in drug design. Molecular dynamics simulations using a quantum mechanics/molecular mechanics potential, with correlated ab initio single point corrections, identify and quantify the subtle determinants of the experimentally observed difference in efficiency. The rate-determining step involves the formation of an enolate intermediate: more efficient stabilization of the enolate and transition state of the key step in MtDHQ2, mainly by the essential residues Tyr24 and Arg19, makes it more efficient than HpDHQ2. Further, a water molecule, which is absent in MtDHQ2 but involved in generation of the catalytic Tyr22 tyrosinate in HpDHQ2, was found to destabilize both the transition state and the enolate intermediate. The quantification of the contribution of key residues and water molecules in the rate-determining step of the mechanism also leads to improved understanding of higher potencies and specificity of known inhibitors, which should aid ongoing inhibitor design.

Tunable, rare earth-doped solid state lasers

DOEpatents

Emmett, John L.; Jacobs, Ralph R.; Krupke, William F.; Weber, Marvin J.

1980-01-01

Laser apparatus comprising combinations of an excimer pump laser and a rare earth-doped solid matrix, utilizing the 5d-4f radiative transition in a rare earth ion to produce visible and ultra-violet laser radiation with high overall efficiency in selected cases and relatively long radiative lifetimes.

Optical Characterization and 2,525 micron Lasing of Cr(2+):Cd(0.85)Mn(0.15)Te

NASA Technical Reports Server (NTRS)

Davis, V. R.; Wu, X.; Hoemmerich, U.; Trivedi, S. B.; Grasza, K.; Yu, Z.

1997-01-01

Transition metal doped solids are of significant current interest for the development of tunable solid-state lasers for the near and mid-infrared (1-4 pm) spectral region. Applications of these lasers include basic research in atomic, molecular, and solid-state physics, optical communication, medicine, and environmental studies of the atmosphere. In transition metal based laser materials, absorption and emission of light arises from electronic transitions between crystal field split energy levels of 3d transition metal ions. The optical spectra generally exhibit broad bands due to the strong interaction between dopant and host (electron-phonon coupling). Broad emission bands offer the prospect of tunable laser activity over a wide wavelength range, e.g. the tuning range of Ti:Sapphire extends from 700-1100 run. The only current transition metal laser operating in the mid-infrared wavelength region (1.8-2.4 micro-m) is CO(2+):MgF2, but its performance is severely limited due to strong nonradiative decay at room temperature. Based on lifetime data, the quantum efficiency is estimated to be less than 3 deg/0 11,21. In general, the probability for non-radiative decay via multi-phonon relaxation increases with decreasing energy gap between ground and excited state. Therefore, efficient transition metal lasers beyond -1.6 micro-m are rare. Recently, tunable laser activity around 2.3 micro-m was observed from Cr doped ZnS and ZnSe. The new lasing center in these materials was identified as Cr(2+) occupying the tetrahedral Zn site. Tetrahedrally coordinated optical centers are rather unusual among transition metal lasers. Their potential usefulness, however, has been demonstrated by the recent development of near infrared laser materials such as Cr:forsterite and Cr:YAG, which are based on tetrahedrally coordinated Cr(4+) ions. According to the Laporte selection rule, electric-dipole transition within the optically active 3d-electron shells are parity forbidden. However, a static acentric electric crystal field or the coupling of asymmetric phonons can force electric-dipole transitions by the admixture of wave functions with opposite parity. Tetrahedral sites lack inversion symmetry which provides the odd-parity field necessary to relax the parity selection rule. Therefore, high absorption and emission cross sections are observed. An enhanced radiative emission rate is also expected to reduce the detrimental effect of non-radiative decay. Motivated by the initial results on Cr doped ZnS and ZnSe, we have started a comprehensive effort to study Cr(2+) doped II-VI semiconductors for solid-state laser applications. In this paper we present the optical properties and the demonstration of mid-infrared lasing from Cr doped Cd(0.85)Mn(0.15)Te.

Statistical mechanics of complex economies

NASA Astrophysics Data System (ADS)

Bardoscia, Marco; Livan, Giacomo; Marsili, Matteo

2017-04-01

In the pursuit of ever increasing efficiency and growth, our economies have evolved to remarkable degrees of complexity, with nested production processes feeding each other in order to create products of greater sophistication from less sophisticated ones, down to raw materials. The engine of such an expansion have been competitive markets that, according to general equilibrium theory (GET), achieve efficient allocations under specific conditions. We study large random economies within the GET framework, as templates of complex economies, and we find that a non-trivial phase transition occurs: the economy freezes in a state where all production processes collapse when either the number of primary goods or the number of available technologies fall below a critical threshold. As in other examples of phase transitions in large random systems, this is an unintended consequence of the growth in complexity. Our findings suggest that the Industrial Revolution can be regarded as a sharp transition between different phases, but also imply that well developed economies can collapse if too many intermediate goods are introduced.

Exciton fission in monolayer transition metal dichalcogenide semiconductors.

PubMed

Steinhoff, A; Florian, M; Rösner, M; Schönhoff, G; Wehling, T O; Jahnke, F

2017-10-27

When electron-hole pairs are excited in a semiconductor, it is a priori not clear if they form a plasma of unbound fermionic particles or a gas of composite bosons called excitons. Usually, the exciton phase is associated with low temperatures. In atomically thin transition metal dichalcogenide semiconductors, excitons are particularly important even at room temperature due to strong Coulomb interaction and a large exciton density of states. Using state-of-the-art many-body theory, we show that the thermodynamic fission-fusion balance of excitons and electron-hole plasma can be efficiently tuned via the dielectric environment as well as charge carrier doping. We propose the observation of these effects by studying exciton satellites in photoemission and tunneling spectroscopy, which present direct solid-state counterparts of high-energy collider experiments on the induced fission of composite particles.

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

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

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE PAGES

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

2018-02-19

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Triplet photosensitizers: from molecular design to applications.

PubMed

Zhao, Jianzhang; Wu, Wanhua; Sun, Jifu; Guo, Song

2013-06-21

Triplet photosensitizers (PSs) are compounds that can be efficiently excited to the triplet excited state which subsequently act as catalysts in photochemical reactions. The name is originally derived from compounds that were used to transfer the triplet energy to other compounds that have only a small intrinsic triplet state yield. Triplet PSs are not only used for triplet energy transfer, but also for photocatalytic organic reactions, photodynamic therapy (PDT), photoinduced hydrogen production from water and triplet-triplet annihilation (TTA) upconversion. A good PS should exhibit strong absorption of the excitation light, a high yield of intersystem crossing (ISC) for efficient production of the triplet state, and a long triplet lifetime to allow for the reaction with a reactant molecule. Most transition metal complexes show efficient ISC, but small molar absorption coefficients in the visible spectral region and short-lived triplet excited states, which make them unsuitable as triplet PSs. One obstacle to the development of new triplet PSs is the difficulty in predicting the ISC of chromophores, especially of organic compounds without any heavy atoms. This review article summarizes some molecular design rationales for triplet PSs, based on the molecular structural factors that facilitate ISC. The design of transition metal complexes with large molar absorption coefficients in the visible spectral region and long-lived triplet excited states is presented. A new method of using a spin converter to construct heavy atom-free organic triplet PSs is discussed, with which ISC becomes predictable, C60 being an example. To enhance the performance of triplet PSs, energy funneling based triplet PSs are proposed, which show broadband absorption in the visible region. Applications of triplet PSs in photocatalytic organic reactions, hydrogen production, triplet-triplet annihilation upconversion and luminescent oxygen sensing are briefly introduced.

Second derivatives for approximate spin projection methods

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

Thompson, Lee M.; Hratchian, Hrant P., E-mail: hhratchian@ucmerced.edu

2015-02-07

The use of broken-symmetry electronic structure methods is required in order to obtain correct behavior of electronically strained open-shell systems, such as transition states, biradicals, and transition metals. This approach often has issues with spin contamination, which can lead to significant errors in predicted energies, geometries, and properties. Approximate projection schemes are able to correct for spin contamination and can often yield improved results. To fully make use of these methods and to carry out exploration of the potential energy surface, it is desirable to develop an efficient second energy derivative theory. In this paper, we formulate the analytical secondmore » derivatives for the Yamaguchi approximate projection scheme, building on recent work that has yielded an efficient implementation of the analytical first derivatives.« less

Stark tuning and electrical charge state control of single divacancies in silicon carbide

NASA Astrophysics Data System (ADS)

de las Casas, Charles F.; Christle, David J.; Ul Hassan, Jawad; Ohshima, Takeshi; Son, Nguyen T.; Awschalom, David D.

2017-12-01

Neutrally charged divacancies in silicon carbide (SiC) are paramagnetic color centers whose long coherence times and near-telecom operating wavelengths make them promising for scalable quantum communication technologies compatible with existing fiber optic networks. However, local strain inhomogeneity can randomly perturb their optical transition frequencies, which degrades the indistinguishability of photons emitted from separate defects and hinders their coupling to optical cavities. Here, we show that electric fields can be used to tune the optical transition frequencies of single neutral divacancy defects in 4H-SiC over a range of several GHz via the DC Stark effect. The same technique can also control the charge state of the defect on microsecond timescales, which we use to stabilize unstable or non-neutral divacancies into their neutral charge state. Using fluorescence-based charge state detection, we show that both 975 nm and 1130 nm excitation can prepare their neutral charge state with near unity efficiency.

Discriminative Cooperative Networks for Detecting Phase Transitions

NASA Astrophysics Data System (ADS)

Liu, Ye-Hua; van Nieuwenburg, Evert P. L.

2018-04-01

The classification of states of matter and their corresponding phase transitions is a special kind of machine-learning task, where physical data allow for the analysis of new algorithms, which have not been considered in the general computer-science setting so far. Here we introduce an unsupervised machine-learning scheme for detecting phase transitions with a pair of discriminative cooperative networks (DCNs). In this scheme, a guesser network and a learner network cooperate to detect phase transitions from fully unlabeled data. The new scheme is efficient enough for dealing with phase diagrams in two-dimensional parameter spaces, where we can utilize an active contour model—the snake—from computer vision to host the two networks. The snake, with a DCN "brain," moves and learns actively in the parameter space, and locates phase boundaries automatically.

The existence of superconductivity in Nb1.75Ta0.25PdS5

NASA Astrophysics Data System (ADS)

Venkateshwarlu, D.; Patidar, Manju Mishra; Singh, Durgesh; Amarendra, G.; Ganesan, V.

2018-05-01

Nb2PdS5 is a novel superconductor having promising potential for applications. Synthesis of this by solid state reaction, characterization using susceptibility and resistivity of Ta substituted Nb2PdS5 is reported in the present paper. Nb1.75Ta0.25PdS5 shows a diamagnetic transition at 6K while the onset of superconducting transition in resistivity is found at 6.73K; the slight difference is attributed to Aslamazov-Larkin paraconductivity fluctuations. This can be ascertained from the fact that the transition seen in resistivity is so broad that the zero resistance state is elusive due to weak inter grain coupling. We also report temperature dependence of resistivity under magnetic fields up to 16T that shows considerable broadening in fields that can be attributed to the field induced resistive state with underlying vortex motion. The results are explained based on models like thermally activated flux flow (TAFF) in the light of Kramer's relation. The normal state just above Tc has a negative temperature co-efficient of resistivity reminiscent of the Anderson localization scenario. The estimated critical field of 27T is more than two times higher than that of Pauli limit.

Formation of AlCl by radiative association

NASA Astrophysics Data System (ADS)

Andreazza, C. M.; de Almeida, A. A.; Vichietti, R. M.

2018-06-01

The rate coefficient for the formation of aluminium monochloride, AlCl, from the radiative association of aluminium and chlorine atoms is estimated as a function of temperature. The coupling of the Al and Cl atoms through the A1Π molecular electronic state, which undergoes radiative transition to the X1Σ+ ground state, is the most efficient transition to form AlCl. The rate constant was found to vary with temperature according to the expressions k(T) = 1.22 × 10-16(T/300)0.40exp (-748/T) cm3 s-1 for temperatures between 300 and 1000 K, and k(T) = 2.20 × 10-16(T/300)0.175exp (-1067/T) cm3 s-1 for temperatures between 1000 and 14 000 K.

Complex band structures of transition metal dichalcogenide monolayers with spin-orbit coupling effects

NASA Astrophysics Data System (ADS)

Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

2016-09-01

Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin-orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed.

Stabilized 1762 nm Laser for Barium Ion Qubit Readout via Adiabatic Passage

NASA Astrophysics Data System (ADS)

Salacka, Joanna

2008-05-01

Trapped ions are one of the most promising candidates for the implementation of quantum computation. We are trapping single ions of Ba^137 to serve as our qubit, because the hyperfine structure of its ground state and its various visible-wavelength transitions make it favorable for quantum computation. The two hyperfine ground levels will serve as our |1> and |0> qubit states. The readout of the qubit will be accomplished by first selectively shelving the ion directly to the metastable 5D5/2 state using a 1762 nm narrow band fiber laser. Next, the cooling and repumping lasers are turned on and the fluorescence of the ion is measured. Since the 5D5/2 state is decoupled from the laser cooling transitions, the ion will remain dark when shelved. Thus if fluorescence is seen we know that the qubit was in the |0> state, and if no fluorescence is seen it was in the |1> state. The laser is actively stabilized to a temperature-controlled, high-finesse 1.76 um Zerodur optical cavity. The shelving to the 5D5/2 state is most efficiently achieved with adiabatic passage, which requires a smooth scan of the laser frequency across the transition resonance. To accomplish this, the laser frequency is modulated by an AOM driven by a smooth frequency sweep of adjustable amplitude and duration.

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).

Efficient characterisation of large deviations using population dynamics

NASA Astrophysics Data System (ADS)

Brewer, Tobias; Clark, Stephen R.; Bradford, Russell; Jack, Robert L.

2018-05-01

We consider population dynamics as implemented by the cloning algorithm for analysis of large deviations of time-averaged quantities. We use the simple symmetric exclusion process with periodic boundary conditions as a prototypical example and investigate the convergence of the results with respect to the algorithmic parameters, focussing on the dynamical phase transition between homogeneous and inhomogeneous states, where convergence is relatively difficult to achieve. We discuss how the performance of the algorithm can be optimised, and how it can be efficiently exploited on parallel computing platforms.

Proof of Concept for Efficient Application of Quantum Chemical Techniques to Model Enviromental Mercury Depletion Reactions Through Transition State Theory

DTIC Science & Technology

2018-01-02

Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10...Collaborators: Award Information Award Number ARO W911NF-16-1-0486 Title of Research Proof of Concept for Efficient Application of Quantum...figure out the feasibility of the interconversion between the two forms of mercury. For this purpose, we mainly deal with the experimental studies of

Formal methods for test case generation

NASA Technical Reports Server (NTRS)

Rushby, John (Inventor); De Moura, Leonardo Mendonga (Inventor); Hamon, Gregoire (Inventor)

2011-01-01

The invention relates to the use of model checkers to generate efficient test sets for hardware and software systems. The method provides for extending existing tests to reach new coverage targets; searching *to* some or all of the uncovered targets in parallel; searching in parallel *from* some or all of the states reached in previous tests; and slicing the model relative to the current set of coverage targets. The invention provides efficient test case generation and test set formation. Deep regions of the state space can be reached within allotted time and memory. The approach has been applied to use of the model checkers of SRI's SAL system and to model-based designs developed in Stateflow. Stateflow models achieving complete state and transition coverage in a single test case are reported.

Study on optoelectronic properties of Spiro-CN for developing an efficient OLED

NASA Astrophysics Data System (ADS)

Mishra, Ashok Kumar

2018-05-01

There are a class of organic molecules and polymers which exhibit semiconductor behavior because of nearly free conjugate π-electrons. Hopping of these electrons in molecules forms different excited singlet and triplet states named as excitons. Some of these organic molecules can be set to emit photons by triplet-singlet excitonic transition via a process called Thermally Activated Delayed Fluorescence (TADF) which is exploited for designing the Organic Light Emitting diode (OLED.) Spiro-CN (spirobifluorene skeletons) Spiro is one of these reported noble metal-free TADF molecules which offers unique optical and electronic properties arising from the efficient transition and reverse intersystem crossing between the lowest singlet (S) and triplet (T) excited states. Its ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T→S) could directly impact their properties and performances, which is attractive for a wide variety of low-cost optoelectronic device. In the present study, the Spiro-CN compounds have been taken up for the investigation of various optoelectronic properties including the thermally activated delayed fluorescence (TADF) by using the Koopmans Method and Density Functional Theory. The present study discusses the utility of the Spiro-CN organic semiconductor as a suitable TADF material essential for developing an efficient Organic Light Emitting Diode (OLED).

NonMarkov Ito Processes with 1- state memory

NASA Astrophysics Data System (ADS)

McCauley, Joseph L.

2010-08-01

A Markov process, by definition, cannot depend on any previous state other than the last observed state. An Ito process implies the Fokker-Planck and Kolmogorov backward time partial differential eqns. for transition densities, which in turn imply the Chapman-Kolmogorov eqn., but without requiring the Markov condition. We present a class of Ito process superficially resembling Markov processes, but with 1-state memory. In finance, such processes would obey the efficient market hypothesis up through the level of pair correlations. These stochastic processes have been mislabeled in recent literature as 'nonlinear Markov processes'. Inspired by Doob and Feller, who pointed out that the ChapmanKolmogorov eqn. is not restricted to Markov processes, we exhibit a Gaussian Ito transition density with 1-state memory in the drift coefficient that satisfies both of Kolmogorov's partial differential eqns. and also the Chapman-Kolmogorov eqn. In addition, we show that three of the examples from McKean's seminal 1966 paper are also nonMarkov Ito processes. Last, we show that the transition density of the generalized Black-Scholes type partial differential eqn. describes a martingale, and satisfies the ChapmanKolmogorov eqn. This leads to the shortest-known proof that the Green function of the Black-Scholes eqn. with variable diffusion coefficient provides the so-called martingale measure of option pricing.

On the reversibility of transitions between closed and open cellular convection

DOE PAGES

Feingold, G.; Koren, I.; Yamaguchi, T.; ...

2015-07-08

The two-way transition between closed and open cellular convection is addressed in an idealized cloud-resolving modeling framework. A series of cloud-resolving simulations shows that the transition between closed and open cellular states is asymmetrical and characterized by a rapid ("runaway") transition from the closed- to the open-cell state but slower recovery to the closed-cell state. Given that precipitation initiates the closed–open cell transition and that the recovery requires a suppression of the precipitation, we apply an ad hoc time-varying drop concentration to initiate and suppress precipitation. We show that the asymmetry in the two-way transition occurs even for very rapidmore » drop concentration replenishment. The primary barrier to recovery is the loss in turbulence kinetic energy (TKE) associated with the loss in cloud water (and associated radiative cooling) and the vertical stratification of the boundary layer during the open-cell period. In transitioning from the open to the closed state, the system faces the task of replenishing cloud water fast enough to counter precipitation losses, such that it can generate radiative cooling and TKE. It is hampered by a stable layer below cloud base that has to be overcome before water vapor can be transported more efficiently into the cloud layer. Recovery to the closed-cell state is slower when radiative cooling is inefficient such as in the presence of free tropospheric clouds or after sunrise, when it is hampered by the absorption of shortwave radiation. Tests suggest that recovery to the closed-cell state is faster when the drizzle is smaller in amount and of shorter duration, i.e., when the precipitation causes less boundary layer stratification. Cloud-resolving model results on recovery rates are supported by simulations with a simple predator–prey dynamical system analogue. It is suggested that the observed closing of open cells by ship effluent likely occurs when aerosol intrusions are large, when contact comes prior to the heaviest drizzle in the early morning hours, and when the free troposphere is cloud free.« less

The Metric System: Preparing Your Students for the Big Change

ERIC Educational Resources Information Center

Social Education, 1974

1974-01-01

Information sources to assist teachers and students in making a smooth and efficient transition to the metric system include an annotated bibliography of literature dealing with the history and present state of measurement in the U.S., with the metric system generally, and with problems involved in metric conversion. (Author/KM)

Methods for finding transition states on reduced potential energy surfaces

NASA Astrophysics Data System (ADS)

Burger, Steven K.; Ayers, Paul W.

2010-06-01

Three new algorithms are presented for determining transition state (TS) structures on the reduced potential energy surface, that is, for problems in which a few important degrees of freedom can be isolated. All three methods use constrained optimization to rapidly find the TS without an initial Hessian evaluation. The algorithms highlight how efficiently the TS can be located on a reduced surface, where the rest of the degrees of freedom are minimized. The first method uses a nonpositive definite quasi-Newton update for the reduced degrees of freedom. The second uses Shepard interpolation to fit the Hessian and starts from a set of points that bound the TS. The third directly uses a finite difference scheme to calculate the reduced degrees of freedom of the Hessian of the entire system, and searches for the TS on the full potential energy surface. All three methods are tested on an epoxide hydrolase cluster, and the ring formations of cyclohexane and cyclobutenone. The results indicate that all the methods are able to converge quite rapidly to the correct TS, but that the finite difference approach is the most efficient.

Methods for finding transition states on reduced potential energy surfaces.

PubMed

Burger, Steven K; Ayers, Paul W

2010-06-21

Three new algorithms are presented for determining transition state (TS) structures on the reduced potential energy surface, that is, for problems in which a few important degrees of freedom can be isolated. All three methods use constrained optimization to rapidly find the TS without an initial Hessian evaluation. The algorithms highlight how efficiently the TS can be located on a reduced surface, where the rest of the degrees of freedom are minimized. The first method uses a nonpositive definite quasi-Newton update for the reduced degrees of freedom. The second uses Shepard interpolation to fit the Hessian and starts from a set of points that bound the TS. The third directly uses a finite difference scheme to calculate the reduced degrees of freedom of the Hessian of the entire system, and searches for the TS on the full potential energy surface. All three methods are tested on an epoxide hydrolase cluster, and the ring formations of cyclohexane and cyclobutenone. The results indicate that all the methods are able to converge quite rapidly to the correct TS, but that the finite difference approach is the most efficient.

Faster photosynthetic induction in tobacco by expressing cyanobacterial flavodiiron proteins in chloroplasts.

PubMed

Gómez, Rodrigo; Carrillo, Néstor; Morelli, María P; Tula, Suresh; Shahinnia, Fahimeh; Hajirezaei, Mohammad-Reza; Lodeyro, Anabella F

2018-05-01

Plants grown in the field experience sharp changes in irradiation due to shading effects caused by clouds, other leaves, etc. The excess of absorbed light energy is dissipated by a number of mechanisms including cyclic electron transport, photorespiration, and Mehler-type reactions. This protection is essential for survival but decreases photosynthetic efficiency. All phototrophs except angiosperms harbor flavodiiron proteins (Flvs) which relieve the excess of excitation energy on the photosynthetic electron transport chain by reducing oxygen directly to water. Introduction of cyanobacterial Flv1/Flv3 in tobacco chloroplasts resulted in transgenic plants that showed similar photosynthetic performance under steady-state illumination, but displayed faster recovery of various photosynthetic parameters, including electron transport and non-photochemical quenching during dark-light transitions. They also kept the electron transport chain in a more oxidized state and enhanced the proton motive force of dark-adapted leaves. The results indicate that, by acting as electron sinks during light transitions, Flvs contribute to increase photosynthesis protection and efficiency under changing environmental conditions as those found by plants in the field.

Slow cooling and efficient extraction of C-exciton hot carriers in MoS2 monolayer

PubMed Central

Wang, Lei; Wang, Zhuo; Wang, Hai-Yu; Grinblat, Gustavo; Huang, Yu-Li; Wang, Dan; Ye, Xiao-Hui; Li, Xian-Bin; Bao, Qiaoliang; Wee, AndrewThye-Shen; Maier, Stefan A; Chen, Qi-Dai; Zhong, Min-Lin; Qiu, Cheng-Wei; Sun, Hong-Bo

2017-01-01

In emerging optoelectronic applications, such as water photolysis, exciton fission and novel photovoltaics involving low-dimensional nanomaterials, hot-carrier relaxation and extraction mechanisms play an indispensable and intriguing role in their photo-electron conversion processes. Two-dimensional transition metal dichalcogenides have attracted much attention in above fields recently; however, insight into the relaxation mechanism of hot electron-hole pairs in the band nesting region denoted as C-excitons, remains elusive. Using MoS2 monolayers as a model two-dimensional transition metal dichalcogenide system, here we report a slower hot-carrier cooling for C-excitons, in comparison with band-edge excitons. We deduce that this effect arises from the favourable band alignment and transient excited-state Coulomb environment, rather than solely on quantum confinement in two-dimension systems. We identify the screening-sensitive bandgap renormalization for MoS2 monolayer/graphene heterostructures, and confirm the initial hot-carrier extraction for the C-exciton state with an unprecedented efficiency of 80%, accompanied by a twofold reduction in the exciton binding energy. PMID:28054546

Feedback-controlled radiation pressure cooling

NASA Astrophysics Data System (ADS)

Prior, Yehiam; Vilensky, Mark; Averbukh, Ilya Sh.

2008-03-01

We propose a new approach to laser cooling of micromechanical devices, which is based on the phenomenon of optical bistability. These devices are modeled as a Fabry-Perot resonator with one fixed and one oscillating mirror. The bistability may be induced by an external feedback loop. When excited by an external laser, the cavity field has two co-existing stable steady-states depending on the position of the moving mirror. If the latter moves slow enough, the field in the cavity adjusts itself adiabatically to the mirror's instantaneous position. The mirror experiences radiation pressure corresponding to the intensity value. A sharp transition between two values of the radiation pressure force happens twice per every period of the mirror oscillation at non-equivalent positions (hysteresis effect), which leads to a non-zero net energy loss. The cooling mechanism resembles Sisyphus cooling in which the cavity mode performs sudden transitions between two stable states. We provide a dynamical stability analysis of the coupled moving mirror -- cavity field system, and find the parameters for efficient cooling. Direct numerical simulations show that a bistable cavity provides much more efficient cooling compared to the regular one.

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.

Functional Analyses of the Plant Photosystem I–Light-Harvesting Complex II Supercomplex Reveal That Light-Harvesting Complex II Loosely Bound to Photosystem II Is a Very Efficient Antenna for Photosystem I in State II[W

PubMed Central

Galka, Pierre; Santabarbara, Stefano; Khuong, Thi Thu Huong; Degand, Hervé; Morsomme, Pierre; Jennings, Robert C.; Boekema, Egbert J.; Caffarri, Stefano

2012-01-01

State transitions are an important photosynthetic short-term response that allows energy distribution balancing between photosystems I (PSI) and II (PSII). In plants when PSII is preferentially excited compared with PSI (State II), part of the major light-harvesting complex LHCII migrates to PSI to form a PSI-LHCII supercomplex. So far, little is known about this complex, mainly due to purification problems. Here, a stable PSI-LHCII supercomplex is purified from Arabidopsis thaliana and maize (Zea mays) plants. It is demonstrated that LHCIIs loosely bound to PSII in State I are the trimers mainly involved in state transitions and become strongly bound to PSI in State II. Specific Lhcb1-3 isoforms are differently represented in the mobile LHCII compared with S and M trimers. Fluorescence analyses indicate that excitation energy migration from mobile LHCII to PSI is rapid and efficient, and the quantum yield of photochemical conversion of PSI-LHCII is substantially unaffected with respect to PSI, despite a sizable increase of the antenna size. An updated PSI-LHCII structural model suggests that the low-energy chlorophylls 611 and 612 in LHCII interact with the chlorophyll 11145 at the interface of PSI. In contrast with the common opinion, we suggest that the mobile pool of LHCII may be considered an intimate part of the PSI antenna system that is displaced to PSII in State I. PMID:22822202

Solar-pumped gas laser development

NASA Technical Reports Server (NTRS)

Wilson, J. W.

1981-01-01

The direct conversion of solar radiation into an inverted population for extraction in an optical cavity holds promise as a relatively simple system design. Broad-band photoabsorption in the visible or near-UV range is required to excite large volumes of gas and to ensure good solar absorption efficiency. The state excited must be a metastable state which is not quenched by the parent gas. The emission bandwidth must be less than approximately 10 A. The system should show chemical reversibility and an insensitivity to increasing temperature. Other properties such as good quantum efficiency and kinetic efficiency are also implied. A search of electronic-vibrational transitions in diatomic molecules satisfying these conditions is now in progress. A photodissociation-pumped atomic iodine laser is now being tested under solar pumping conditions. Photodissociation studies for thallium spin-flip metastable formation will begin in the near future.

System and method of vehicle operating condition management

DOEpatents

Sujan, Vivek A.; Vajapeyazula, Phani; Follen, Kenneth; Wu, An; Moffett, Barty L.

2015-10-20

A vehicle operating condition profile can be determined over a given route while also considering imposed constraints such as deviation from time targets, deviation from maximum governed speed limits, etc. Given current vehicle speed, engine state and transmission state, the present disclosure optimally manages the engine map and transmission to provide a recommended vehicle operating condition that optimizes fuel consumption in transitioning from one vehicle state to a target state. Exemplary embodiments provide for offline and online optimizations relative to fuel consumption. The benefit is increased freight efficiency in transporting cargo from source to destination by minimizing fuel consumption and maintaining drivability.

Efficient repumping of a Ca magneto-optical trap

NASA Astrophysics Data System (ADS)

Mills, Michael; Puri, Prateek; Yu, Yanmei; Derevianko, Andrei; Schneider, Christian; Hudson, Eric R.

2017-09-01

We investigate the limiting factors in the standard implementation of the Ca magneto-optical trap. We find that intercombination transitions from the 4 s 5 p 1P1 state used to repump the electronic population from the 3 d 4 s 1D2 state severely reduce the trap lifetime. We explore seven alternative repumping schemes theoretically and investigate five of them experimentally. We find that all five of these schemes yield a significant increase in the trap lifetime and consequently improve the number of atoms and peak atom density by as much as ˜20 times and ˜6 times, respectively. One of these transitions, at 453 nm, is shown to approach the fundamental limit for a Ca magneto-optical trap with repumping only from the dark 3 d 4 s 1D2 state, yielding a trap lifetime of ˜5 s.

Allocating dissipation across a molecular machine cycle to maximize flux

PubMed Central

Brown, Aidan I.; Sivak, David A.

2017-01-01

Biomolecular machines consume free energy to break symmetry and make directed progress. Nonequilibrium ATP concentrations are the typical free energy source, with one cycle of a molecular machine consuming a certain number of ATP, providing a fixed free energy budget. Since evolution is expected to favor rapid-turnover machines that operate efficiently, we investigate how this free energy budget can be allocated to maximize flux. Unconstrained optimization eliminates intermediate metastable states, indicating that flux is enhanced in molecular machines with fewer states. When maintaining a set number of states, we show that—in contrast to previous findings—the flux-maximizing allocation of dissipation is not even. This result is consistent with the coexistence of both “irreversible” and reversible transitions in molecular machine models that successfully describe experimental data, which suggests that, in evolved machines, different transitions differ significantly in their dissipation. PMID:29073016

Coherent manipulation of a solid-state artificial atom with few photons.

PubMed

Giesz, V; Somaschi, N; Hornecker, G; Grange, T; Reznychenko, B; De Santis, L; Demory, J; Gomez, C; Sagnes, I; Lemaître, A; Krebs, O; Lanzillotti-Kimura, N D; Lanco, L; Auffeves, A; Senellart, P

2016-06-17

In a quantum network based on atoms and photons, a single atom should control the photon state and, reciprocally, a single photon should allow the coherent manipulation of the atom. Both operations require controlling the atom environment and developing efficient atom-photon interfaces, for instance by coupling the natural or artificial atom to cavities. So far, much attention has been drown on manipulating the light field with atomic transitions, recently at the few-photon limit. Here we report on the reciprocal operation and demonstrate the coherent manipulation of an artificial atom by few photons. We study a quantum dot-cavity system with a record cooperativity of 13. Incident photons interact with the atom with probability 0.95, which radiates back in the cavity mode with probability 0.96. Inversion of the atomic transition is achieved for 3.8 photons on average, showing that our artificial atom performs as if fully isolated from the solid-state environment.

Trivalent cerium coped crystals as tunable laser systems: two bad apples

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

Hamilton, D.S.

1985-01-01

The 5d-4f transitions of trivalent doped crystals have broad emission bands with large oscillator strengths and near unity quantum efficiency. These characteristics make cerium systems strong candidates for tunable solid state lasers. However, two such cerium crystals will probably never lase. The first is Ce/sup 3 +/:YAG where a strong excited state absorption quenches the lasing transition. Our recent measurements have indicated that the excited state absorption terminates in the YAG conduction band with a peak cross section of 1.0 x 10/sup -17/ cm/sup 2/ at 700 nm. Some of the general features of impurity ion to band spectra aremore » discussed. The second system is Ce/sup 3 +/:CaF/sub 2/ where a uv pump induced photochromic center is produced following excitation of the cerium ions. The initial measurements of cerium related transient absorptions in Ce/sup 3 +/:YLF are also presented.« less

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

Three-photon resonance ionization of atomic Mn in a hot-cavity laser ion source using Ti:sapphire lasers

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

Liu, Y.; Gottwald, T.; Mattolat, C.

We have demonstrated three-photon resonance ionization of atomic manganese (Mn) in a hot-cavity ion source using Ti: sapphire lasers. Three-step ionization schemes employing different intermediate levels and Rydberg or autoionizing (AI) states in the final ionization step are established. Strong AI resonances were observed via the 3d 54s5s f 6S 5/2 level at 49 415.35 cm -1, while Rydberg transitions were reached from the 3d 54s4d e 6D 9/2,7/2,5/2) levels at around 47 210 cm -1. Analyses of the strong Rydberg transitions associated with the 3d 54s4d e 6D 7/2 lower level indicate that they belong to the dipole-allowed 4dmore » → nf 6F° 9/2,7/2,5/2 series converging to the 3d 54s 7S 3 ground state of Mn II. From this series, an ionization potential of 59 959.56 ± 0.01 cm -1 is obtained for Mn. At high ion source temperatures the semi-forbidden 4d → nf 8 F°9/2,7/2,5/2 series was also observed. The overall ionization efficiency for Mn has been measured to be about 0.9% when using the strong AI transition in the third excitation step and 0.3% when employing an intense Rydberg transition. Experimental data indicate that the ionization efficiency was limited by the interaction of Mn atoms with ion source materials at high temperatures.« less

Three-photon resonance ionization of atomic Mn in a hot-cavity laser ion source using Ti:sapphire lasers

DOE PAGES

Liu, Y.; Gottwald, T.; Mattolat, C.; ...

2015-05-08

We have demonstrated three-photon resonance ionization of atomic manganese (Mn) in a hot-cavity ion source using Ti: sapphire lasers. Three-step ionization schemes employing different intermediate levels and Rydberg or autoionizing (AI) states in the final ionization step are established. Strong AI resonances were observed via the 3d 54s5s f 6S 5/2 level at 49 415.35 cm -1, while Rydberg transitions were reached from the 3d 54s4d e 6D 9/2,7/2,5/2) levels at around 47 210 cm -1. Analyses of the strong Rydberg transitions associated with the 3d 54s4d e 6D 7/2 lower level indicate that they belong to the dipole-allowed 4dmore » → nf 6F° 9/2,7/2,5/2 series converging to the 3d 54s 7S 3 ground state of Mn II. From this series, an ionization potential of 59 959.56 ± 0.01 cm -1 is obtained for Mn. At high ion source temperatures the semi-forbidden 4d → nf 8 F°9/2,7/2,5/2 series was also observed. The overall ionization efficiency for Mn has been measured to be about 0.9% when using the strong AI transition in the third excitation step and 0.3% when employing an intense Rydberg transition. Experimental data indicate that the ionization efficiency was limited by the interaction of Mn atoms with ion source materials at high temperatures.« less

Wnt/β-catenin signaling promotes self-renewal and inhibits the primed state transition in naïve human embryonic stem cells.

PubMed

Xu, Zhuojin; Robitaille, Aaron M; Berndt, Jason D; Davidson, Kathryn C; Fischer, Karin A; Mathieu, Julie; Potter, Jennifer C; Ruohola-Baker, Hannele; Moon, Randall T

2016-10-18

In both mice and humans, pluripotent stem cells (PSCs) exist in at least two distinct states of pluripotency, known as the naïve and primed states. Our understanding of the intrinsic and extrinsic factors that enable PSCs to self-renew and to transition between different pluripotent states is important for understanding early development. In mouse embryonic stem cells (mESCs), Wnt proteins stimulate mESC self-renewal and support the naïve state. In human embryonic stem cells (hESCs), Wnt/β-catenin signaling is active in naïve-state hESCs and is reduced or absent in primed-state hESCs. However, the role of Wnt/β-catenin signaling in naïve hESCs remains largely unknown. Here, we demonstrate that inhibition of the secretion of Wnts or inhibition of the stabilization of β-catenin in naïve hESCs reduces cell proliferation and colony formation. Moreover, we show that addition of recombinant Wnt3a partially rescues cell proliferation in naïve hESCs caused by inhibition of Wnt secretion. Notably, inhibition of Wnt/β-catenin signaling in naïve hESCs did not cause differentiation. Instead, it induced primed hESC-like proteomic and metabolic profiles. Thus, our results suggest that naïve hESCs secrete Wnts that activate autocrine or paracrine Wnt/β-catenin signaling to promote efficient self-renewal and inhibit the transition to the primed state.

2.097μ Cth:YAG flashlamp pumped high energy high efficiency laser operation (patent pending)

NASA Astrophysics Data System (ADS)

Bar-Joseph, Dan

2018-02-01

Flashlamp pumped Cth:YAG lasers are mainly used in medical applications (urology). The main laser transition is at 2.13μ and is called a quasi-three level having an emission cross-section of 7x10-21 cm2 and a ground state absorption of approximately 5%/cm. Because of the relatively low absorption, combined with a modest emission cross-section, the laser requires high reflectivity output coupling, and therefore high intra-cavity energy density which limits the output to approximately 4J/pulse for reliable operation. This paper will describe a method of efficiently generating high output energy at low intra-cavity energy density by using an alternative 2.097μ transition having an emission cross-section of 5x10-21 cm2 and a ground level absorption of approximately 14%/cm.

Optimal Charge-to-Spin Conversion in Graphene on Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Offidani, Manuel; Milletarı, Mirco; Raimondi, Roberto; Ferreira, Aires

2017-11-01

When graphene is placed on a monolayer of semiconducting transition metal dichalcogenide (TMD) its band structure develops rich spin textures due to proximity spin-orbital effects with interfacial breaking of inversion symmetry. In this work, we show that the characteristic spin winding of low-energy states in graphene on a TMD monolayer enables current-driven spin polarization, a phenomenon known as the inverse spin galvanic effect (ISGE). By introducing a proper figure of merit, we quantify the efficiency of charge-to-spin conversion and show it is close to unity when the Fermi level approaches the spin minority band. Remarkably, at high electronic density, even though subbands with opposite spin helicities are occupied, the efficiency decays only algebraically. The giant ISGE predicted for graphene on TMD monolayers is robust against disorder and remains large at room temperature.

Polynomial-time quantum algorithm for the simulation of chemical dynamics

PubMed Central

Kassal, Ivan; Jordan, Stephen P.; Love, Peter J.; Mohseni, Masoud; Aspuru-Guzik, Alán

2008-01-01

The computational cost of exact methods for quantum simulation using classical computers grows exponentially with system size. As a consequence, these techniques can be applied only to small systems. By contrast, we demonstrate that quantum computers could exactly simulate chemical reactions in polynomial time. Our algorithm uses the split-operator approach and explicitly simulates all electron-nuclear and interelectronic interactions in quadratic time. Surprisingly, this treatment is not only more accurate than the Born–Oppenheimer approximation but faster and more efficient as well, for all reactions with more than about four atoms. This is the case even though the entire electronic wave function is propagated on a grid with appropriately short time steps. Although the preparation and measurement of arbitrary states on a quantum computer is inefficient, here we demonstrate how to prepare states of chemical interest efficiently. We also show how to efficiently obtain chemically relevant observables, such as state-to-state transition probabilities and thermal reaction rates. Quantum computers using these techniques could outperform current classical computers with 100 qubits. PMID:19033207

Zipping and Unzipping of Adenylate Kinase: Atomistic Insights into the Ensemble of Open ↔ Closed Transitions

PubMed Central

Beckstein, Oliver; Denning, Elizabeth J.; Perilla, Juan R.; Woolf, Thomas B.

2009-01-01

Adenylate kinase (AdK), a phosphotransferase enzyme, plays an important role in cellular energy homeostasis. It undergoes a large conformational change between an open and a closed state, even in the absence of substrate. We investigate the apo-AdK transition at the atomic level both with free energy calculations and our new dynamic importance sampling (DIMS) molecular dynamics (MD) method. DIMS is shown to sample biologically relevant conformations as verified by comparing an ensemble of hundreds of DIMS transitions to AdK crystal structure intermediates. The simulations reveal in atomic detail how hinge regions partially and intermittently unfold during the transition. Conserved salt bridges are seen to have important structural and dynamic roles; in particular four ionic bonds are identified that open in a sequential, zipper-like fashion and thus dominate the free energy landscape of the transition. Transitions between the closed and open conformations only have to overcome moderate free energy barriers. Unexpectedly, the closed and open state encompass broad free energy basins that contain conformations differing in domain hinge motions by up to 40°. The significance of these extended states is discussed in relation to recent experimental FRET measurements. Taken together, these results demonstrate how a small number of cooperative key interactions can shape the overall dynamics of an enzyme and suggest an “all-or-nothing” mechanism for the opening and closing of AdK. Our efficient DIMS-MD computer simulation approach can provide a detailed picture of a functionally important macromolecular transition and thus help to interpret and suggest experiments to probe the conformational landscape of dynamic proteins such as AdK. PMID:19751742

Unambiguously identifying spin states of transition-metal ions in the Earth (Invited)

NASA Astrophysics Data System (ADS)

Hsu, H.

2010-12-01

The spin state of a transition-metal ion in crystalline solids, defined by the number of unpaired electrons in the ion’s incomplete 3d shell, may vary with many factors, such as temperature, pressure, strain, and the local atomic configuration, to name a few. Such a phenomenon, known as spin-state crossover, plays a crucial role in spintronic materials. Recently, the pressure-induced spin-state crossover in iron-bearing minerals has been recognized to affect the minerals’ structural and elastic properties. However, the detailed mechanism of such crossover in iron-bearing magnesium silicate perovskite, the most abundant mineral in the Earth, remains unclear. A significant part of this confusion arises from the difficulty in reliably extracting the spin state from experiments. For the same reason, the thermally-induced spin-state crossover in lanthanum cobaltite (LaCoO3) has been controversial for more than four decades. In this talk, I will discuss how first-principle calculations can help clarifying these long-standing controversies. In addition to the total energy, equation of state, and elastic properties of each spin state, first-principle calculations also predict the electric field gradient (EFG) at the nucleus of each transition-metal ion. Our calculations showed that the nuclear EFG, a quantity that can be measured via Mössbauer or nuclear magnetic resonance (NMR) spectroscopy, depends primarily on the spin state, irrespective of the concentration or configuration of transition-metal ions. Such robustness makes EFG a unique fingerprint to identify the spin state. The combination of first-principle calculations and Mössbauer/NMR spectroscopy can therefore be a reliable and efficient approach in tackling spin-state crossover problems in the Earth. This work was primarily supported by the MRSEC Program of NSF under Awards Number DMR-0212302 and DMR-0819885, and partially supported by NSF under ATM-0428774 (V-Lab), EAR-1019853, and EAR-0810272. The computations were performed mainly at the Minnesota Supercomputing Institute (MSI).

Direct electron-impact mechanism of excitation of mercury monobromide in a double-pulse dielectric-barrier-discharge HgBr lamp

NASA Astrophysics Data System (ADS)

Datsyuk, V. V.; Izmailov, I. A.; Naumov, V. V.; Kochelap, V. A.

2016-08-01

In a nonequlibrium plasma of a gas-discharge HgBr lamp, the terminal electronic state of the HgBr(B-X) radiative transition with a peak wavelength of 502 nm remains populated for a relatively long time and is repeatedly excited to the B state in collisions with plasma electrons. This transfer of the HgBr molecules from the ground state X to the excited state B is the main mechanism of formation of the light-emitting molecules especially when the lamp is excited by double current pulses. According to our simulations, due to the electron-induced transitions between HgBr(X) and HgBr(B), the output characteristics of the DBD lamp operating in a double-pulse regime are better than those of the lamp operating in a single-pulse regime. In the considered case, the peak power is calculated to increase by a factor of about 2 and the lamp efficiency increases by about 50%.

Selectivity for CO2 over CH4 on a functionalized periodic mesoporous phenylene-silica explained by transition state theory

NASA Astrophysics Data System (ADS)

Kunkel, Christian; Viñes, Francesc; Lourenço, Mirtha A. O.; Ferreira, Paula; Gomes, José R. B.; Illas, Francesc

2017-03-01

Efficient separation of CO2/CH4 is critical in biogas upgrading, requiring highly selective adsorbents. Based on the adsorption energies of -0.30 and -0.14 eV, previously calculated by dispersion corrected density functional theory for adsorption/desorption of CO2 and CH4 on the functionalized periodic mesoporous phenylene-silica material APTMS@Ph-PMO, respectively, transition state theory rates were derived and used to simulate the adsorption/desorption rates of these two gases on APTMS@Ph-PMO. The latter yielded an estimation of initial CO2/CH4 selectivity at various temperatures. At T = 298 K, selectivity of 32.2 agrees to an experimental value of 26.1, which validates the method used for evaluating CO2/CH4 adsorption selectivities.

Correlation of Hydrogen-Atom Abstraction Reaction Efficiencies for Aryl Radicals with their Vertical Electron Affinities and the Vertical Ionization Energies of the Hydrogen Atom Donors

PubMed Central

Jing, Linhong; Nash, John J.

2009-01-01

The factors that control the reactivities of aryl radicals toward hydrogen-atom donors were studied by using a dual-cell Fourier-transform ion cyclotron resonance mass spectrometer (FT – ICR). Hydrogen-atom abstraction reaction efficiencies for two substrates, cyclohexane and isopropanol, were measured for twenty-three structurally different, positively-charged aryl radicals, which included dehydrobenzenes, dehydronaphthalenes, dehydropyridines, and dehydro(iso)quinolines. A logarithmic correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) vertical electron affinities (EA) of the aryl radicals. Transition state energies calculated for three of the aryl radicals with isopropanol were found to correlate linearly with their (calculated) EAs. No correlation was found between the hydrogen-atom abstraction reaction efficiencies and the (calculated) enthalpy changes for the reactions. Measurement of the reaction efficiencies for the reactions of several different hydrogen-atom donors with a few selected aryl radicals revealed a logarithmic correlation between the hydrogen-atom abstraction reaction efficiencies and the vertical ionization energies (IE) of the hydrogen-atom donors, but not the lowest homolytic X – H (X = heavy atom) bond dissociation energies of the hydrogen-atom donors. Examination of the hydrogen-atom abstraction reactions of twenty-nine different aryl radicals and eighteen different hydrogen-atom donors showed that the reaction efficiency increases (logarithmically) as the difference between the IE of the hydrogen-atom donor and the EA of the aryl radical decreases. This dependence is likely to result from the increasing polarization, and concomitant stabilization, of the transition state as the energy difference between the neutral and ionic reactants decreases. Thus, the hydrogen-atom abstraction reaction efficiency for an aryl radical can be “tuned” by structural changes that influence either the vertical EA of the aryl radical or the vertical IE of the hydrogen atom donor. PMID:19061320

Non-resonant electromechanical energy harvesting using inter-ferroelectric phase transitions

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

Pérez Moyet, Richard; Rossetti, George A., E-mail: george.rossetti-jr@uconn.edu; Stace, Joseph

Non-resonant electromechanical energy harvesting is demonstrated under low frequency excitation (<50 Hz) using [110]{sub C}-poled lead indium niobate-lead magnesium niobate-lead titanate relaxor ferroelectric single crystals with compositions near the morphotropic phase boundary. The efficiency of power generation at the stress-induced phase transition between domain-engineered rhombohedral and orthorhombic ferroelectric states is as much as four times greater than is obtained in the linear piezoelectric regime under identical measurement conditions but during loading below the coercive stress of the phase change. The phase transition mode of electromechanical transduction holds potential for non-resonant energy harvesting from low-frequency vibrations and does not require mechanical frequencymore » up-conversion.« less

Sparsity-weighted outlier FLOODing (OFLOOD) method: Efficient rare event sampling method using sparsity of distribution.

PubMed

Harada, Ryuhei; Nakamura, Tomotake; Shigeta, Yasuteru

2016-03-30

As an extension of the Outlier FLOODing (OFLOOD) method [Harada et al., J. Comput. Chem. 2015, 36, 763], the sparsity of the outliers defined by a hierarchical clustering algorithm, FlexDice, was considered to achieve an efficient conformational search as sparsity-weighted "OFLOOD." In OFLOOD, FlexDice detects areas of sparse distribution as outliers. The outliers are regarded as candidates that have high potential to promote conformational transitions and are employed as initial structures for conformational resampling by restarting molecular dynamics simulations. When detecting outliers, FlexDice defines a rank in the hierarchy for each outlier, which relates to sparsity in the distribution. In this study, we define a lower rank (first ranked), a medium rank (second ranked), and the highest rank (third ranked) outliers, respectively. For instance, the first-ranked outliers are located in a given conformational space away from the clusters (highly sparse distribution), whereas those with the third-ranked outliers are nearby the clusters (a moderately sparse distribution). To achieve the conformational search efficiently, resampling from the outliers with a given rank is performed. As demonstrations, this method was applied to several model systems: Alanine dipeptide, Met-enkephalin, Trp-cage, T4 lysozyme, and glutamine binding protein. In each demonstration, the present method successfully reproduced transitions among metastable states. In particular, the first-ranked OFLOOD highly accelerated the exploration of conformational space by expanding the edges. In contrast, the third-ranked OFLOOD reproduced local transitions among neighboring metastable states intensively. For quantitatively evaluations of sampled snapshots, free energy calculations were performed with a combination of umbrella samplings, providing rigorous landscapes of the biomolecules. © 2015 Wiley Periodicals, Inc.

Kinetic energy classification and smoothing for compact B-spline basis sets in quantum Monte Carlo

DOE PAGES

Krogel, Jaron T.; Reboredo, Fernando A.

2018-01-25

Quantum Monte Carlo calculations of defect properties of transition metal oxides have become feasible in recent years due to increases in computing power. As the system size has grown, availability of on-node memory has become a limiting factor. Saving memory while minimizing computational cost is now a priority. The main growth in memory demand stems from the B-spline representation of the single particle orbitals, especially for heavier elements such as transition metals where semi-core states are present. Despite the associated memory costs, splines are computationally efficient. In this paper, we explore alternatives to reduce the memory usage of splined orbitalsmore » without significantly affecting numerical fidelity or computational efficiency. We make use of the kinetic energy operator to both classify and smooth the occupied set of orbitals prior to splining. By using a partitioning scheme based on the per-orbital kinetic energy distributions, we show that memory savings of about 50% is possible for select transition metal oxide systems. Finally, for production supercells of practical interest, our scheme incurs a performance penalty of less than 5%.« less

Kinetic energy classification and smoothing for compact B-spline basis sets in quantum Monte Carlo

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

Krogel, Jaron T.; Reboredo, Fernando A.

Quantum Monte Carlo calculations of defect properties of transition metal oxides have become feasible in recent years due to increases in computing power. As the system size has grown, availability of on-node memory has become a limiting factor. Saving memory while minimizing computational cost is now a priority. The main growth in memory demand stems from the B-spline representation of the single particle orbitals, especially for heavier elements such as transition metals where semi-core states are present. Despite the associated memory costs, splines are computationally efficient. In this paper, we explore alternatives to reduce the memory usage of splined orbitalsmore » without significantly affecting numerical fidelity or computational efficiency. We make use of the kinetic energy operator to both classify and smooth the occupied set of orbitals prior to splining. By using a partitioning scheme based on the per-orbital kinetic energy distributions, we show that memory savings of about 50% is possible for select transition metal oxide systems. Finally, for production supercells of practical interest, our scheme incurs a performance penalty of less than 5%.« less

Kinetic energy classification and smoothing for compact B-spline basis sets in quantum Monte Carlo

NASA Astrophysics Data System (ADS)

Krogel, Jaron T.; Reboredo, Fernando A.

2018-01-01

Quantum Monte Carlo calculations of defect properties of transition metal oxides have become feasible in recent years due to increases in computing power. As the system size has grown, availability of on-node memory has become a limiting factor. Saving memory while minimizing computational cost is now a priority. The main growth in memory demand stems from the B-spline representation of the single particle orbitals, especially for heavier elements such as transition metals where semi-core states are present. Despite the associated memory costs, splines are computationally efficient. In this work, we explore alternatives to reduce the memory usage of splined orbitals without significantly affecting numerical fidelity or computational efficiency. We make use of the kinetic energy operator to both classify and smooth the occupied set of orbitals prior to splining. By using a partitioning scheme based on the per-orbital kinetic energy distributions, we show that memory savings of about 50% is possible for select transition metal oxide systems. For production supercells of practical interest, our scheme incurs a performance penalty of less than 5%.

Heralded Quantum Gate between Remote Quantum Memories

DTIC Science & Technology

2009-06-25

emission fre- quency. Second, the geometrical modes from the two fibers are matched to better than 98% as characterized with laser light. Third, the...remains in the trap for several weeks. Doppler-cooling by laser light slightly red detuned from the 2S1=2 $ 2P1=2 transition at 369.5 nm localizes the ions...state decays to the metastable 2D3=2 level. This level is depopulated with a laser near 935.2 nm to maintain efficient cooling and state detection. We

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.

Solar-pumped gas laser development

NASA Technical Reports Server (NTRS)

Wilson, J. W.

1980-01-01

A survey of gas properties through detailed kinetic models led to the identification of critical gas parameters for use in choosing appropriate gas combinations for solar pumped lasers. Broadband photoabsorption in the visible or near UV range is required to excite large volumes of gas and to insure good solar absorption efficiency. The photoexcitation density is independent of the absorption bandwidth. The state excited must be a metastable state which is not quenched by the parent gas. The emission bandwidth must be less than 10 A to insure lasing threshold over reasonable gain lengths. The system should show a high degree of chemical reversibility and an insensitivity to increasing temperature. Other properties such as good quantum efficiency and kinetic efficiency are also implied. Although photoexcitation of electronic vibrational transitions is considered as a possible system if the emission bands sufficiently narrow, it appears that photodissociation into atomic metastables is more likely to result in a successful solar pumped laser system.

Enhanced sampling of molecular dynamics simulation of peptides and proteins by double coupling to thermal bath.

PubMed

Chen, Changjun; Huang, Yanzhao; Xiao, Yi

2013-01-01

Low sampling efficiency in conformational space is the well-known problem for conventional molecular dynamics. It greatly increases the difficulty for molecules to find the transition path to native state, and costs amount of CPU time. To accelerate the sampling, in this paper, we re-couple the critical degrees of freedom in the molecule to environment temperature, like dihedrals in generalized coordinates or nonhydrogen atoms in Cartesian coordinate. After applying to ALA dipeptide model, we find that this modified molecular dynamics greatly enhances the sampling behavior in the conformational space and provides more information about the state-to-state transition, while conventional molecular dynamics fails to do so. Moreover, from the results of 16 independent 100 ns simulations by the new method, it shows that trpzip2 has one-half chances to reach the naive state in all the trajectories, which is greatly higher than conventional molecular dynamics. Such an improvement would provide a potential way for searching the conformational space or predicting the most stable states of peptides and proteins.

Slow-light-enhanced upconversion for photovoltaic applications in one-dimensional photonic crystals.

PubMed

Johnson, Craig M; Reece, Peter J; Conibeer, Gavin J

2011-10-15

We present an approach to realizing enhanced upconversion efficiency in erbium (Er)-doped photonic crystals. Slow-light-mode pumping of the first Er excited state transition can result in enhanced emission from higher-energy levels that may lead to finite subbandgap external quantum efficiency in crystalline silicon solar cells. Using a straightforward electromagnetic model, we calculate potential field enhancements of more than 18× within he slow-light mode of a one-dimensional photonic crystal and discuss design trade-offs and considerations for photovoltaics.

An all-solid-state perovskite-sensitized solar cell based on the dual function polyaniline as the sensitizer and p-type hole-transporting material

NASA Astrophysics Data System (ADS)

Xiao, Yaoming; Han, Gaoyi; Chang, Yunzhen; Zhou, Haihan; Li, Miaoyu; Li, Yanping

2014-12-01

High performance dual function of polyaniline (PANI) with brachyplast structure is synthesized by using a two-step cyclic voltammetry (CV) approach onto the fluorinated tin oxide (FTO) glass substrate, which acts as the sensitizer and p-type hole-transporting material (p-HTM) for the all-solid-state perovskite-sensitized solar cell (ass-PSSC) due to its π-π* transition and the localized polaron. The ass-PSSC based on the PANI delivers a photovoltaic conversion efficiency of 7.34%, and reduces from 7.34% to 6.71% after 1000 h, thereby 91.42% of the energy conversion efficiency is kept, indicating the device has a good long-term stability.

Quantum tunneling of oxygen atoms on very cold surfaces.

PubMed

Minissale, M; Congiu, E; Baouche, S; Chaabouni, H; Moudens, A; Dulieu, F; Accolla, M; Cazaux, S; Manicó, G; Pirronello, V

2013-08-02

Any evolving system can change state via thermal mechanisms (hopping a barrier) or via quantum tunneling. Most of the time, efficient classical mechanisms dominate at high temperatures. This is why an increase of the temperature can initiate the chemistry. We present here an experimental investigation of O-atom diffusion and reactivity on water ice. We explore the 6-25 K temperature range at submonolayer surface coverages. We derive the diffusion temperature law and observe the transition from quantum to classical diffusion. Despite the high mass of O, quantum tunneling is efficient even at 6 K. As a consequence, the solid-state astrochemistry of cold regions should be reconsidered and should include the possibility of forming larger organic molecules than previously expected.

Tunneling anisotropic magnetoresistance driven by magnetic phase transition.

PubMed

Chen, X Z; Feng, J F; Wang, Z C; Zhang, J; Zhong, X Y; Song, C; Jin, L; Zhang, B; Li, F; Jiang, M; Tan, Y Z; Zhou, X J; Shi, G Y; Zhou, X F; Han, X D; Mao, S C; Chen, Y H; Han, X F; Pan, F

2017-09-06

The independent control of two magnetic electrodes and spin-coherent transport in magnetic tunnel junctions are strictly required for tunneling magnetoresistance, while junctions with only one ferromagnetic electrode exhibit tunneling anisotropic magnetoresistance dependent on the anisotropic density of states with no room temperature performance so far. Here, we report an alternative approach to obtaining tunneling anisotropic magnetoresistance in α'-FeRh-based junctions driven by the magnetic phase transition of α'-FeRh and resultantly large variation of the density of states in the vicinity of MgO tunneling barrier, referred to as phase transition tunneling anisotropic magnetoresistance. The junctions with only one α'-FeRh magnetic electrode show a magnetoresistance ratio up to 20% at room temperature. Both the polarity and magnitude of the phase transition tunneling anisotropic magnetoresistance can be modulated by interfacial engineering at the α'-FeRh/MgO interface. Besides the fundamental significance, our finding might add a different dimension to magnetic random access memory and antiferromagnet spintronics.Tunneling anisotropic magnetoresistance is promising for next generation memory devices but limited by the low efficiency and functioning temperature. Here the authors achieved 20% tunneling anisotropic magnetoresistance at room temperature in magnetic tunnel junctions with one α'-FeRh magnetic electrode.

Bacteriorhodopsin Material and Film Fabrication Issues for Holographic Applications

NASA Technical Reports Server (NTRS)

Downie, John D.; Timucin, Dogan A.; Smithey, Daniel T.; Crew, Marshall; Rayfield, George W.; Lan, Sonie (Technical Monitor)

1998-01-01

We discuss issues associated with bacteriorhodopsin (BR) materials and films that affect optical performance in holographic applications. For the D85N variant, some critical parameters include degree of hydration and recording wavelength. The quantum efficiency of the molecular state transition is observed to be apparently dependent on the illumination wavelength. We explain this effect by modeling the photo-activity of the D85N variant as two competing photocycles between the 9-cis and 13-cis retinal configurations. We are able to determine the pure excited P-state absorbance spectrum from the ground state spectrum and mixed population spectra obtained by bleaching to steady-state conditions.

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.

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.

Solid state RF power: The route to 1W per euro cent

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

Heid, Oliver

2013-04-19

In most particle accelerators RF power is a decisive design constraint due to high costs and relative inflexibility of current electron beam based RF sources, i.e. Klystrons, Magnetrons, Tetrodes etc. At VHF/UHF frequencies the transition to solid state devices promises to fundamentally change the situation. Recent progress brings 1 Watt per Euro cent installed cost within reach. We present a Silicon Carbide semiconductor solution utilising the Solid State Direct Drive technology at unprecedented efficiency, power levels and power densities. The proposed solution allows retrofitting of existing RF accelerators and opens the route to novel particle accelerator concepts.

Control of the metal-insulator transition in vanadium dioxide by modifying orbital occupancy

NASA Astrophysics Data System (ADS)

Aetukuri, Nagaphani B.; Gray, Alexander X.; Drouard, Marc; Cossale, Matteo; Gao, Li; Reid, Alexander H.; Kukreja, Roopali; Ohldag, Hendrik; Jenkins, Catherine A.; Arenholz, Elke; Roche, Kevin P.; Dürr, Hermann A.; Samant, Mahesh G.; Parkin, Stuart S. P.

2013-10-01

External control of the conductivity of correlated oxides is one of the most promising schemes for realizing energy-efficient electronic devices. Vanadium dioxide (VO2), an archetypal correlated oxide compound, undergoes a temperature-driven metal-insulator transition near room temperature with a concomitant change in crystal symmetry. Here, we show that the metal-insulator transition temperature of thin VO2(001) films can be changed continuously from ~285 to ~345K by varying the thickness of the RuO2 buffer layer (resulting in different epitaxial strains). Using strain-, polarization- and temperature-dependent X-ray absorption spectroscopy, in combination with X-ray diffraction and electronic transport measurements, we demonstrate that the transition temperature and the structural distortion across the transition depend on the orbital occupancy in the metallic state. Our findings open up the possibility of controlling the conductivity in atomically thin VO2 layers by manipulating the orbital occupancy by, for example, heterostructural engineering.

Electron-Phonon Coupling and Resonant Relaxation from 1D and 1P States in PbS Quantum Dots.

PubMed

Kennehan, Eric R; Doucette, Grayson S; Marshall, Ashley R; Grieco, Christopher; Munson, Kyle T; Beard, Matthew C; Asbury, John B

2018-05-31

Observations of the hot-phonon bottleneck, which is predicted to slow the rate of hot carrier cooling in quantum confined nanocrystals, have been limited to date for reasons that are not fully understood. We used time-resolved infrared spectroscopy to directly measure higher energy intraband transitions in PbS colloidal quantum dots. Direct measurements of these intraband transitions permitted detailed analysis of the electronic overlap of the quantum confined states that may influence their relaxation processes. In smaller PbS nanocrystals, where the hot-phonon bottleneck is expected to be most pronounced, we found that relaxation of parity selection rules combined with stronger electron-phonon coupling led to greater spectral overlap of transitions among the quantum confined states. This created pathways for fast energy transfer and relaxation that may bypass the predicted hot-phonon bottleneck. In contrast, larger, but still quantum confined nanocrystals did not exhibit such relaxation of the parity selection rules and possessed narrower intraband states. These observations were consistent with slower relaxation dynamics that have been measured in larger quantum confined systems. These findings indicated that, at small radii, electron-phonon interactions overcome the advantageous increase in energetic separation of the electronic states for PbS quantum dots. Selection of appropriately sized quantum dots, which minimize spectral broadening due to electron-phonon interactions while maximizing electronic state separation, is necessary to observe the hot-phonon bottleneck. Such optimization may provide a framework for achieving efficient hot carrier collection and multiple exciton generation.

Finite Correlation Length Implies Efficient Preparation of Quantum Thermal States

NASA Astrophysics Data System (ADS)

Brandão, Fernando G. S. L.; Kastoryano, Michael J.

2018-05-01

Preparing quantum thermal states on a quantum computer is in general a difficult task. We provide a procedure to prepare a thermal state on a quantum computer with a logarithmic depth circuit of local quantum channels assuming that the thermal state correlations satisfy the following two properties: (i) the correlations between two regions are exponentially decaying in the distance between the regions, and (ii) the thermal state is an approximate Markov state for shielded regions. We require both properties to hold for the thermal state of the Hamiltonian on any induced subgraph of the original lattice. Assumption (ii) is satisfied for all commuting Gibbs states, while assumption (i) is satisfied for every model above a critical temperature. Both assumptions are satisfied in one spatial dimension. Moreover, both assumptions are expected to hold above the thermal phase transition for models without any topological order at finite temperature. As a building block, we show that exponential decay of correlation (for thermal states of Hamiltonians on all induced subgraphs) is sufficient to efficiently estimate the expectation value of a local observable. Our proof uses quantum belief propagation, a recent strengthening of strong sub-additivity, and naturally breaks down for states with topological order.

Does a full-time, 24-hour intensivist improve care and efficiency?

PubMed

Carlson, R W; Weiland, D E; Srivathsan, K

1996-07-01

This article reviews the hypothesis that staffing with full-time intensive care physicians leads to improvements in the management of ICUs and in the outcome for ICU patients. Variations in the professional organization of critical care units in the United States are discussed. The advantages and disadvantages of open, closed, and transitional (comanagement) ICU organizational structures are presented.

Diffusion pseudotime robustly reconstructs lineage branching.

PubMed

Haghverdi, Laleh; Büttner, Maren; Wolf, F Alexander; Buettner, Florian; Theis, Fabian J

2016-10-01

The temporal order of differentiating cells is intrinsically encoded in their single-cell expression profiles. We describe an efficient way to robustly estimate this order according to diffusion pseudotime (DPT), which measures transitions between cells using diffusion-like random walks. Our DPT software implementations make it possible to reconstruct the developmental progression of cells and identify transient or metastable states, branching decisions and differentiation endpoints.

Understanding molecular motor walking along a microtubule: a themosensitive asymmetric Brownian motor driven by bubble formation.

PubMed

Arai, Noriyoshi; Yasuoka, Kenji; Koishi, Takahiro; Ebisuzaki, Toshikazu; Zeng, Xiao Cheng

2013-06-12

The "asymmetric Brownian ratchet model", a variation of Feynman's ratchet and pawl system, is invoked to understand the kinesin walking behavior along a microtubule. The model system, consisting of a motor and a rail, can exhibit two distinct binding states, namely, the random Brownian state and the asymmetric potential state. When the system is transformed back and forth between the two states, the motor can be driven to "walk" in one direction. Previously, we suggested a fundamental mechanism, that is, bubble formation in a nanosized channel surrounded by hydrophobic atoms, to explain the transition between the two states. In this study, we propose a more realistic and viable switching method in our computer simulation of molecular motor walking. Specifically, we propose a thermosensitive polymer model with which the transition between the two states can be controlled by temperature pulses. Based on this new motor system, the stepping size and stepping time of the motor can be recorded. Remarkably, the "walking" behavior observed in the newly proposed model resembles that of the realistic motor protein. The bubble formation based motor not only can be highly efficient but also offers new insights into the physical mechanism of realistic biomolecule motors.

New stable tunable solid-state dye laser in the red

NASA Astrophysics Data System (ADS)

Gvishi, Raz; Reisfeld, Renata; Burshtein, Zeev; Miron, Eli

1993-08-01

A red perylene derivative was impregnated into a composite silica-gel glass, and characterized as a dye laser material. The absorption spectrum in the range 480 - 600 nm belongs to the S0 - S1 electronic transition, with a structure reflecting the perylene skeletal vibrations, of typical energy 1100 - 1200 cm-1. An additional peak between 400 and 460 nm belongs to the S0 - S2 transition. The fluorescence exhibits a mirror image relative to the S0 - S1 absorption, with a Stokes shift of about 40 nm for the 0 - 0 transition. Laser tunability was obtained in the range 605 - 630 nm using a frequency-doubled Nd:YAG laser for pumping ((lambda) equals 532 nm). This wavelength range is important for medical applications, such as photodynamic therapy of some cancer tumors. Maximum laser efficiency of approximately 2.5% was obtained at 617 nm. Maximum output was approximately 0.36 mJ/pulse at a repetition rate of 10 Hz. Minimum laser threshold obtained was 0.45 mJ/pulse. The medium losses are attributed to an excited-state singlet-singlet absorption, with an upper limit cross-section of approximately 2.5 X 10-16 cm2. The laser output was stable over more than approximately 500,000 pulses, under excitation with the green line of a copper vapor laser (510 nm), of energy density approximately 40 mJ/cm2 per pulse. Good prospects exist for a considerable enhancement in laser output efficiency.

A steep-slope transistor based on abrupt electronic phase transition

NASA Astrophysics Data System (ADS)

Shukla, Nikhil; Thathachary, Arun V.; Agrawal, Ashish; Paik, Hanjong; Aziz, Ahmedullah; Schlom, Darrell G.; Gupta, Sumeet Kumar; Engel-Herbert, Roman; Datta, Suman

2015-08-01

Collective interactions in functional materials can enable novel macroscopic properties like insulator-to-metal transitions. While implementing such materials into field-effect-transistor technology can potentially augment current state-of-the-art devices by providing unique routes to overcome their conventional limits, attempts to harness the insulator-to-metal transition for high-performance transistors have experienced little success. Here, we demonstrate a pathway for harnessing the abrupt resistivity transformation across the insulator-to-metal transition in vanadium dioxide (VO2), to design a hybrid-phase-transition field-effect transistor that exhibits gate controlled steep (`sub-kT/q') and reversible switching at room temperature. The transistor design, wherein VO2 is implemented in series with the field-effect transistor's source rather than into the channel, exploits negative differential resistance induced across the VO2 to create an internal amplifier that facilitates enhanced performance over a conventional field-effect transistor. Our approach enables low-voltage complementary n-type and p-type transistor operation as demonstrated here, and is applicable to other insulator-to-metal transition materials, offering tantalizing possibilities for energy-efficient logic and memory applications.

A steep-slope transistor based on abrupt electronic phase transition.

PubMed

Shukla, Nikhil; Thathachary, Arun V; Agrawal, Ashish; Paik, Hanjong; Aziz, Ahmedullah; Schlom, Darrell G; Gupta, Sumeet Kumar; Engel-Herbert, Roman; Datta, Suman

2015-08-07

Collective interactions in functional materials can enable novel macroscopic properties like insulator-to-metal transitions. While implementing such materials into field-effect-transistor technology can potentially augment current state-of-the-art devices by providing unique routes to overcome their conventional limits, attempts to harness the insulator-to-metal transition for high-performance transistors have experienced little success. Here, we demonstrate a pathway for harnessing the abrupt resistivity transformation across the insulator-to-metal transition in vanadium dioxide (VO2), to design a hybrid-phase-transition field-effect transistor that exhibits gate controlled steep ('sub-kT/q') and reversible switching at room temperature. The transistor design, wherein VO2 is implemented in series with the field-effect transistor's source rather than into the channel, exploits negative differential resistance induced across the VO2 to create an internal amplifier that facilitates enhanced performance over a conventional field-effect transistor. Our approach enables low-voltage complementary n-type and p-type transistor operation as demonstrated here, and is applicable to other insulator-to-metal transition materials, offering tantalizing possibilities for energy-efficient logic and memory applications.

F -state quenching with CH 4 for buffer-gas cooled 171 Y b + frequency standard [Methane (CH4) for quenching the F-state in trapped Yb+ ions].

DOE PAGES

Jau, Y. -Y.; Hunker, J. D.; Schwindt, P. D. D.

2015-11-01

We report that methane, CH 4, can be used as an efficient F-state quenching gas for trapped ytterbium ions. The quenching rate coefficient is measured to be (2.8 ± 0.3) × 10 6 s -1 Torr -1. For applications that use microwave hyperfine transitions of the ground-state 171Y b ions, the CH4 induced frequency shift coefficient and the decoherence rate coefficient are measured as δν/ν = (-3.6 ± 0.1) × 10 -6 Torr -1 and 1/T2 = (1.5 ± 0.2) × 10 5 s -1 Torr -1. In our buffer-gas cooled 171Y b+ microwave clock system, we find that onlymore » ≤10 -8 Torr of CH 4 is required under normal operating conditions to efficiently clear the F-state and maintain ≥85% of trapped ions in the ground state with insignificant pressure shift and collisional decoherence of the clock resonance.« less

Spin-polarized charge transport in HgTe/CdTe quantum well topological insulator under a ferromagnetic metal strip

NASA Astrophysics Data System (ADS)

Wu, Zhenhua; Luo, Kun; Yu, Jiahan; Wu, Xiaobo; Lin, Liangzhong

2018-02-01

Electron tunneling through a single magnetic barrier in a HgTe topological insulator has been theoretically investigated. We find that the perpendicular magnetic field would not lead to spin-flip of the edge states due to the conservation of the angular moment. By tuning the magnetic field and the Fermi energy, the edge channels can be transited from switch-on states to switch-off states and the current from unpolarized states can be filtered to fully spin polarized states. These features offer us an efficient way to control charge/spin transport in a HgTe/CdTe quantum well, and pave a way to construct the nanoelectronic devices utilizing the topological edge states.

Energy-Efficient Routing and Spectrum Assignment Algorithm with Physical-Layer Impairments Constraint in Flexible Optical Networks

NASA Astrophysics Data System (ADS)

Zhao, Jijun; Zhang, Nawa; Ren, Danping; Hu, Jinhua

2017-12-01

The recently proposed flexible optical network can provide more efficient accommodation of multiple data rates than the current wavelength-routed optical networks. Meanwhile, the energy efficiency has also been a hot topic because of the serious energy consumption problem. In this paper, the energy efficiency problem of flexible optical networks with physical-layer impairments constraint is studied. We propose a combined impairment-aware and energy-efficient routing and spectrum assignment (RSA) algorithm based on the link availability, in which the impact of power consumption minimization on signal quality is considered. By applying the proposed algorithm, the connection requests are established on a subset of network topology, reducing the number of transitions from sleep to active state. The simulation results demonstrate that our proposed algorithm can improve the energy efficiency and spectrum resources utilization with the acceptable blocking probability and average delay.

Coupled-Double-Quantum-Dot Environmental Information Engines: A Numerical Analysis

NASA Astrophysics Data System (ADS)

Tanabe, Katsuaki

2016-06-01

We conduct numerical simulations for an autonomous information engine comprising a set of coupled double quantum dots using a simple model. The steady-state entropy production rate in each component, heat and electron transfer rates are calculated via the probability distribution of the four electronic states from the master transition-rate equations. We define an information-engine efficiency based on the entropy change of the reservoir, implicating power generators that employ the environmental order as a new energy resource. We acquire device-design principles, toward the realization of corresponding practical energy converters, including that (1) higher energy levels of the detector-side reservoir than those of the detector dot provide significantly higher work production rates by faster states' circulation, (2) the efficiency is strongly dependent on the relative temperatures of the detector and system sides and becomes high in a particular Coulomb-interaction strength region between the quantum dots, and (3) the efficiency depends little on the system dot's energy level relative to its reservoir but largely on the antisymmetric relative amplitudes of the electronic tunneling rates.

An integrated condition-monitoring method for a milling process using reduced decomposition features

NASA Astrophysics Data System (ADS)

Liu, Jie; Wu, Bo; Wang, Yan; Hu, Youmin

2017-08-01

Complex and non-stationary cutting chatter affects productivity and quality in the milling process. Developing an effective condition-monitoring approach is critical to accurately identify cutting chatter. In this paper, an integrated condition-monitoring method is proposed, where reduced features are used to efficiently recognize and classify machine states in the milling process. In the proposed method, vibration signals are decomposed into multiple modes with variational mode decomposition, and Shannon power spectral entropy is calculated to extract features from the decomposed signals. Principal component analysis is adopted to reduce feature size and computational cost. With the extracted feature information, the probabilistic neural network model is used to recognize and classify the machine states, including stable, transition, and chatter states. Experimental studies are conducted, and results show that the proposed method can effectively detect cutting chatter during different milling operation conditions. This monitoring method is also efficient enough to satisfy fast machine state recognition and classification.

Quantum mechanical hydrogen tunneling in bacterial copper amine oxidase reaction

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

Murakawa, Takeshi; Okajima, Toshihide; Kuroda, Shun'ichi

A key step decisively affecting the catalytic efficiency of copper amine oxidase is stereospecific abstraction of substrate {alpha}-proton by a conserved Asp residue. We analyzed this step by pre-steady-state kinetics using a bacterial enzyme and stereospecifically deuterium-labeled substrates, 2-phenylethylamine and tyramine. A small and temperature-dependent kinetic isotope effect (KIE) was observed with 2-phenylethylamine, whereas a large and temperature-independent KIE was observed with tyramine in the {alpha}-proton abstraction step, showing that this step is driven by quantum mechanical hydrogen tunneling rather than the classical transition-state mechanism. Furthermore, an Arrhenius-type preexponential factor ratio approaching a transition-state value was obtained in the reactionmore » of a mutant enzyme lacking the critical Asp. These results provide strong evidence for enzyme-enhanced hydrogen tunneling. X-ray crystallographic structures of the reaction intermediates revealed a small difference in the binding mode of distal parts of substrates, which would modulate hydrogen tunneling proceeding through either active or passive dynamics.« less

Interatomic Coulombic decay cascades in multiply excited neon clusters

PubMed Central

Nagaya, K.; Iablonskyi, D.; Golubev, N. V.; Matsunami, K.; Fukuzawa, H.; Motomura, K.; Nishiyama, T.; Sakai, T.; Tachibana, T.; Mondal, S.; Wada, S.; Prince, K. C.; Callegari, C.; Miron, C.; Saito, N.; Yabashi, M.; Demekhin, Ph. V.; Cederbaum, L. S.; Kuleff, A. I.; Yao, M.; Ueda, K.

2016-01-01

In high-intensity laser light, matter can be ionized by direct multiphoton absorption even at photon energies below the ionization threshold. However on tuning the laser to the lowest resonant transition, the system becomes multiply excited, and more efficient, indirect ionization pathways become operative. These mechanisms are known as interatomic Coulombic decay (ICD), where one of the species de-excites to its ground state, transferring its energy to ionize another excited species. Here we show that on tuning to a higher resonant transition, a previously unknown type of interatomic Coulombic decay, intra-Rydberg ICD occurs. In it, de-excitation of an atom to a close-lying Rydberg state leads to electron emission from another neighbouring Rydberg atom. Moreover, systems multiply excited to higher Rydberg states will decay by a cascade of such processes, producing even more ions. The intra-Rydberg ICD and cascades are expected to be ubiquitous in weakly-bound systems exposed to high-intensity resonant radiation. PMID:27917867

Quantum phase transition modulation in an atomtronic Mott switch

NASA Astrophysics Data System (ADS)

McLain, Marie A.; Carr, Lincoln D.

2018-07-01

Mott insulators provide stable quantum states and long coherence times due to small number fluctuations, making them good candidates for quantum memory and atomic circuits. We propose a proof-of-principle for a 1D Mott switch using an ultracold Bose gas and optical lattice. With time-evolving block decimation simulations—efficient matrix product state methods—we design a means for transient parameter characterization via a local excitation for ease of engineering into more complex atomtronics. We perform the switch operation by tuning the intensity of the optical lattice, and thus the interaction strength through a conductance transition due to the confined modifications of the ‘wedding cake’ Mott structure. We demonstrate the time-dependence of Fock state transmission and fidelity of the excitation as a means of tuning up the device in a double well and as a measure of noise performance. Two-point correlations via the g (2) measure provide additional information regarding superfluid fragments on the Mott insulating background due to the confinement of the potential.

Performance measures to assess resiliency and efficiency of transit systems.

DOT National Transportation Integrated Search

2017-03-01

Transit agencies are interested in assessing the short-, mid-, and long-term performance of their infrastructure with the : objective of enhancing resiliency and efficiency. This report addresses three distinct aspects of New Jerseys Transit Syste...

Fast-kick-off monotonically convergent algorithm for searching optimal control fields

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

Liao, Sheng-Lun; Ho, Tak-San; Rabitz, Herschel

2011-09-15

This Rapid Communication presents a fast-kick-off search algorithm for quickly finding optimal control fields in the state-to-state transition probability control problems, especially those with poorly chosen initial control fields. The algorithm is based on a recently formulated monotonically convergent scheme [T.-S. Ho and H. Rabitz, Phys. Rev. E 82, 026703 (2010)]. Specifically, the local temporal refinement of the control field at each iteration is weighted by a fractional inverse power of the instantaneous overlap of the backward-propagating wave function, associated with the target state and the control field from the previous iteration, and the forward-propagating wave function, associated with themore » initial state and the concurrently refining control field. Extensive numerical simulations for controls of vibrational transitions and ultrafast electron tunneling show that the new algorithm not only greatly improves the search efficiency but also is able to attain good monotonic convergence quality when further frequency constraints are required. The algorithm is particularly effective when the corresponding control dynamics involves a large number of energy levels or ultrashort control pulses.« less

Non-Markovian Quantum State Diffusion for temperature-dependent linear spectra of light harvesting aggregates

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

Ritschel, Gerhard; Möbius, Sebastian; Eisfeld, Alexander, E-mail: eisfeld@mpipks-dresden.mpg.de

2015-01-21

Non-Markovian Quantum State Diffusion (NMQSD) has turned out to be an efficient method to calculate excitonic properties of aggregates composed of organic chromophores, taking into account the coupling of electronic transitions to vibrational modes of the chromophores. NMQSD is an open quantum system approach that incorporates environmental degrees of freedom (the vibrations in our case) in a stochastic way. We show in this paper that for linear optical spectra (absorption, circular dichroism), no stochastics is needed, even for finite temperatures. Thus, the spectra can be obtained by propagating a single trajectory. To this end, we map a finite temperature environmentmore » to the zero temperature case using the so-called thermofield method. The resulting equations can then be solved efficiently by standard integrators.« less

Statistical Analysis of the First Passage Path Ensemble of Jump Processes

NASA Astrophysics Data System (ADS)

von Kleist, Max; Schütte, Christof; Zhang, Wei

2018-02-01

The transition mechanism of jump processes between two different subsets in state space reveals important dynamical information of the processes and therefore has attracted considerable attention in the past years. In this paper, we study the first passage path ensemble of both discrete-time and continuous-time jump processes on a finite state space. The main approach is to divide each first passage path into nonreactive and reactive segments and to study them separately. The analysis can be applied to jump processes which are non-ergodic, as well as continuous-time jump processes where the waiting time distributions are non-exponential. In the particular case that the jump processes are both Markovian and ergodic, our analysis elucidates the relations between the study of the first passage paths and the study of the transition paths in transition path theory. We provide algorithms to numerically compute statistics of the first passage path ensemble. The computational complexity of these algorithms scales with the complexity of solving a linear system, for which efficient methods are available. Several examples demonstrate the wide applicability of the derived results across research areas.

Conformational Transition Pathways of Epidermal Growth Factor Receptor Kinase Domain from Multiple Molecular Dynamics Simulations and Bayesian Clustering.

PubMed

Li, Yan; Li, Xiang; Ma, Weiya; Dong, Zigang

2014-08-12

The epidermal growth factor receptor (EGFR) is aberrantly activated in various cancer cells and an important target for cancer treatment. Deep understanding of EGFR conformational changes between the active and inactive states is of pharmaceutical interest. Here we present a strategy combining multiply targeted molecular dynamics simulations, unbiased molecular dynamics simulations, and Bayesian clustering to investigate transition pathways during the activation/inactivation process of EGFR kinase domain. Two distinct pathways between the active and inactive forms are designed, explored, and compared. Based on Bayesian clustering and rough two-dimensional free energy surfaces, the energy-favorable pathway is recognized, though DFG-flip happens in both pathways. In addition, another pathway with different intermediate states appears in our simulations. Comparison of distinct pathways also indicates that disruption of the Lys745-Glu762 interaction is critically important in DFG-flip while movement of the A-loop significantly facilitates the conformational change. Our simulations yield new insights into EGFR conformational transitions. Moreover, our results verify that this approach is valid and efficient in sampling of protein conformational changes and comparison of distinct pathways.

Structure and Inhibition of Quorum Sensing Target from Streptococcus pneumoniae

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

Singh,V.; Shi, W.; Almo, S.

2006-01-01

Streptococcus pneumoniae 5'-methylthioadenosine/S-adenosylhomocysteine hydrolase (MTAN) catalyzes the hydrolytic deadenylation of its substrates to form adenine and 5-methylthioribose or S-ribosylhomocysteine (SRH). MTAN is not found in mammals but is involved in bacterial quorum sensing. MTAN gene disruption affects the growth and pathogenicity of bacteria, making it a target for antibiotic design. Kinetic isotope effects and computational studies have established a dissociative S{sub N}1 transition state for Escherichia coli MTAN, and transition state analogues resembling the transition state are powerful inhibitors of the enzyme [Singh, V., Lee, J. L., Nunez, S., Howell, P. L., and Schramm, V. L. (2005) Biochemistry 44, 11647-11659].more » The sequence of MTAN from S. pneumoniae is 40% identical to that of E. coli MTAN, but S. pneumoniae MTAN exhibits remarkably distinct kinetic and inhibitory properties. 5'-Methylthio-Immucillin-A (MT-ImmA) is a transition state analogue resembling an early S{sub N}1 transition state. It is a weak inhibitor of S. pneumoniae MTAN with a K{sub i} of 1.0 {mu}M. The X-ray structure of S. pneumoniae MTAN with MT-ImmA indicates a dimer with the methylthio group in a flexible hydrophobic pocket. Replacing the methyl group with phenyl (PhT-ImmA), tolyl (p-TolT-ImmA), or ethyl (EtT-ImmA) groups increases the affinity to give K{sub i} values of 335, 60, and 40 nM, respectively. DADMe-Immucillins are geometric and electrostatic mimics of a fully dissociated transition state and bind more tightly than Immucillins. MT-DADMe-Immucillin-A inhibits with a K{sub i} value of 24 nM, and replacing the 5'-methyl group with p-Cl-phenyl (p-Cl-PhT-DADMe-ImmA) gave a K{sub i}* value of 0.36 nM. The inhibitory potential of DADMe-Immucillins relative to the Immucillins supports a fully dissociated transition state structure for S. pneumoniae MTAN. Comparison of active site contacts in the X-ray crystal structures of E. coli and S. pneumoniae MTAN with MT-ImmA would predict equal binding, yet most analogues bind 10{sup 3}-10{sup 4}-fold more tightly to the E. coli enzyme. Catalytic site efficiency is primarily responsible for this difference since k{sub cat}/K{sub m} for S. pneumoniae MTAN is decreased 845-fold relative to that of E. coli MTAN.« less

Remote sensing, geographical information systems, and spatial modeling for analyzing public transit services

NASA Astrophysics Data System (ADS)

Wu, Changshan

Public transit service is a promising transportation mode because of its potential to address urban sustainability. Current ridership of public transit, however, is very low in most urban regions, particularly those in the United States. This woeful transit ridership can be attributed to many factors, among which poor service quality is key. Given this, there is a need for transit planning and analysis to improve service quality. Traditionally, spatially aggregate data are utilized in transit analysis and planning. Examples include data associated with the census, zip codes, states, etc. Few studies, however, address the influences of spatially aggregate data on transit planning results. In this research, previous studies in transit planning that use spatially aggregate data are reviewed. Next, problems associated with the utilization of aggregate data, the so-called modifiable areal unit problem (MAUP), are detailed and the need for fine resolution data to support public transit planning is argued. Fine resolution data is generated using intelligent interpolation techniques with the help of remote sensing imagery. In particular, impervious surface fraction, an important socio-economic indicator, is estimated through a fully constrained linear spectral mixture model using Landsat Enhanced Thematic Mapper Plus (ETM+) data within the metropolitan area of Columbus, Ohio in the United States. Four endmembers, low albedo, high albedo, vegetation, and soil are selected to model heterogeneous urban land cover. Impervious surface fraction is estimated by analyzing low and high albedo endmembers. With the derived impervious surface fraction, three spatial interpolation methods, spatial regression, dasymetric mapping, and cokriging, are developed to interpolate detailed population density. Results suggest that cokriging applied to impervious surface is a better alternative for estimating fine resolution population density. With the derived fine resolution data, a multiple route maximal covering/shortest path (MRMCSP) model is proposed to address the tradeoff between public transit service quality and access coverage in an established bus-based transit system. Results show that it is possible to improve current transit service quality by eliminating redundant or underutilized service stops. This research illustrates that fine resolution data can be efficiently generated to support urban planning, management and analysis. Further, this detailed data may necessitate the development of new spatial optimization models for use in analysis.

Enantioselective Organocatalytic Aminomethylation of Aldehydes: A Role for Ionic Interactions and Efficient Access to β2-Amino Acids

PubMed Central

Chi, Yonggui; Gellman, Samuel H.

2009-01-01

Organocatalytic Mannich addition of aldehydes to a formaldehyde-derived iminium species catalyzed by proline-derived chiral pyrrolidines provides β-amino aldehydes with ≥ 90% ee. Mechanistic analysis of the proline-catalyzed reactions suggests that non-hydrogen-bonded ionic interactions at the Mannich reaction transition state can influence stereochemical outcome. The β-amino aldehydes from our process bear a substituent adjacent to the carbonyl and can be efficiently converted to protected β2-amino acids, which are important building blocks for β-peptide foldamers that display useful biological activities. PMID:16719457

Rhenium-phthalocyanine molecular nanojunction with high magnetic anisotropy and high spin filtering efficiency

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

Li, J.; Institute of Nanomaterial and Nanostructure, Changsha University of Science and Technology, Changsha 410114; Hu, J.

2015-07-20

Using the density functional and non-equilibrium Green's function approaches, we studied the magnetic anisotropy and spin-filtering properties of various transition metal-Phthalocyanine molecular junctions across two Au electrodes. Our important finding is that the Au-RePc-Au junction has both large spin filtering efficiency (>80%) and large magnetic anisotropy energy, which makes it suitable for device applications. To provide insights for the further experimental work, we discussed the correlation between the transport property, magnetic anisotropy, and wave function features of the RePc molecule, and we also illustrated the possibility of controlling its magnetic state.

Model checking for linear temporal logic: An efficient implementation

NASA Technical Reports Server (NTRS)

Sherman, Rivi; Pnueli, Amir

1990-01-01

This report provides evidence to support the claim that model checking for linear temporal logic (LTL) is practically efficient. Two implementations of a linear temporal logic model checker is described. One is based on transforming the model checking problem into a satisfiability problem; the other checks an LTL formula for a finite model by computing the cross-product of the finite state transition graph of the program with a structure containing all possible models for the property. An experiment was done with a set of mutual exclusion algorithms and tested safety and liveness under fairness for these algorithms.

Excitation of vacuum ultraviolet spectra of krypton in a cooled gas discharge

NASA Astrophysics Data System (ADS)

Gerasimov, Gennadii N.; Krylov, Boris E.; Hallin, Reinhold

1995-08-01

Results are presented on the experimental study of VUV spectra of krypton excited by a dc discharge in a capillary tube with the wall cooled to the temperature of liquid nitrogen. We studied the 120-200 nm spectral region corresponding to the transitions between the dimer lowest excited states and the weakly bound ground state, 1u, 0u+ yields 0g+. Electron impact, transferring dimers from the ground state into the excited state, is shown to be an efficient excitation mechanism in the 50-650 Torr and the 10-50 mA pressure and current ranges. The spectra obtained and the calculations made corroborate the high rate of this process.

Error-trellis Syndrome Decoding Techniques for Convolutional Codes

NASA Technical Reports Server (NTRS)

Reed, I. S.; Truong, T. K.

1984-01-01

An error-trellis syndrome decoding technique for convolutional codes is developed. This algorithm is then applied to the entire class of systematic convolutional codes and to the high-rate, Wyner-Ash convolutional codes. A special example of the one-error-correcting Wyner-Ash code, a rate 3/4 code, is treated. The error-trellis syndrome decoding method applied to this example shows in detail how much more efficient syndrome decoding is than Viterbi decoding if applied to the same problem. For standard Viterbi decoding, 64 states are required, whereas in the example only 7 states are needed. Also, within the 7 states required for decoding, many fewer transitions are needed between the states.

Error-trellis syndrome decoding techniques for convolutional codes

NASA Technical Reports Server (NTRS)

Reed, I. S.; Truong, T. K.

1985-01-01

An error-trellis syndrome decoding technique for convolutional codes is developed. This algorithm is then applied to the entire class of systematic convolutional codes and to the high-rate, Wyner-Ash convolutional codes. A special example of the one-error-correcting Wyner-Ash code, a rate 3/4 code, is treated. The error-trellis syndrome decoding method applied to this example shows in detail how much more efficient syndrome decordig is than Viterbi decoding if applied to the same problem. For standard Viterbi decoding, 64 states are required, whereas in the example only 7 states are needed. Also, within the 7 states required for decoding, many fewer transitions are needed between the states.

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.

Polarization-free integrated gallium-nitride photonics

PubMed Central

Bayram, C.; Liu, R.

2017-01-01

Gallium Nitride (GaN) materials are the backbone of emerging solid state lighting. To date, GaN research has been primarily focused on hexagonal phase devices due to the natural crystallization. This approach limits the output power and efficiency of LEDs, particularly in the green spectrum. However, GaN can also be engineered to be in cubic phase. Cubic GaN has a lower bandgap (~200 meV) than hexagonal GaN that enables green LEDs much easily. Besides, cubic GaN has more isotropic properties (smaller effective masses, higher carrier mobility, higher doping efficiency, and higher optical gain than hexagonal GaN), and cleavage planes. Due to phase instability, however, cubic phase materials and devices have remained mostly unexplored. Here we review a new method of cubic phase GaN generation: Hexagonal-to-cubic phase transition, based on novel nano-patterning. We report a new crystallographic modelling of this hexagonal-to-cubic phase transition and systematically study the effects of nano-patterning on the GaN phase transition via transmission electron microscopy and electron backscatter diffraction experiments. In summary, silicon-integrated cubic phase GaN light emitters offer a unique opportunity for exploration in next generation photonics. PMID:29307953

Steady-State Characterization of Bacteriorhodopsin-D85N Photocycle

NASA Technical Reports Server (NTRS)

Timucin, Dogan A.; Downie, John D.; Norvig, Peter (Technical Monitor)

1999-01-01

An operational characterization of the photocycle of the genetic mutant D85N of bacteriorhodopsin, BR-D85N, is presented. Steady-state bleach spectra and pump-probe absorbance data are obtained with thick hydrated films containing BR-D85N embedded in a gelatin host. Simple two- and three-state models are used to analyze the photocycle dynamics and extract relevant information such as pure-state absorption spectra, photochemical-transition quantum efficiencies, and thermal lifetimes of dominant states appearing in the photocycle, the knowledge of which should aid in the analysis of optical recording and retrieval of data in films incorporating this photochromic material. The remarkable characteristics of this material and their implications from the viewpoint of optical data storage and processing are discussed.

Ultrahigh-resolution spectroscopy with atomic or molecular dark resonances: Exact steady-state line shapes and asymptotic profiles in the adiabatic pulsed regime

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

Zanon-Willette, Thomas; Clercq, Emeric de; Arimondo, Ennio

2011-12-15

Exact and asymptotic line shape expressions are derived from the semiclassical density matrix representation describing a set of closed three-level {Lambda} atomic or molecular states including decoherences, relaxation rates, and light shifts. An accurate analysis of the exact steady-state dark-resonance profile describing the Autler-Townes doublet, the electromagnetically induced transparency or coherent population trapping resonance, and the Fano-Feshbach line shape leads to the linewidth expression of the two-photon Raman transition and frequency shifts associated to the clock transition. From an adiabatic analysis of the dynamical optical Bloch equations in the weak field limit, a pumping time required to efficiently trap amore » large number of atoms into a coherent superposition of long-lived states is established. For a highly asymmetrical configuration with different decay channels, a strong two-photon resonance based on a lower states population inversion is established when the driving continuous-wave laser fields are greatly unbalanced. When time separated resonant two-photon pulses are applied in the adiabatic pulsed regime for atomic or molecular clock engineering, where the first pulse is long enough to reach a coherent steady-state preparation and the second pulse is very short to avoid repumping into a new dark state, dark-resonance fringes mixing continuous-wave line shape properties and coherent Ramsey oscillations are created. Those fringes allow interrogation schemes bypassing the power broadening effect. Frequency shifts affecting the central clock fringe computed from asymptotic profiles and related to the Raman decoherence process exhibit nonlinear shapes with the three-level observable used for quantum measurement. We point out that different observables experience different shifts on the lower-state clock transition.« less

Effect of kinetic and electronic energy on the reactions of Mn + with H2, HD, and D2

NASA Astrophysics Data System (ADS)

Elkind, J. L.; Armentrout, P. B.

1986-05-01

Reactions of several electronic states of Mn+ with H2, HD, and D2 have been examined using guided ion beam mass spectroscopy. The excitation function for the ground state of Mn+(7S) has two regions: one of very low reactivity at threshold and another more efficient pathway at higher energies. In contrast, the 5S and 5D states react efficiently at their thermodynamic thresholds. In reaction with HD, the 5S and 5D states produce ≊3 times as much MnH+ as MnD+ in the threshold region. This isotope effect is similar to that seen in previous studies of transition metal ion reactions. Reaction of Mn+(7S) with HD, on the other hand, exhibits an extreme isotope effect such that MnD+ is formed almost exclusively. The state dependence of the reactivity and reaction mechanisms is explained using simple molecular orbital concepts. The results are analyzed to yield a bond dissociation energy at 0 K for MnH+ of 2.06±0.15 eV (47.5±3.4 kcal/mol).

Design of UV laser pulses for the preparation of matrix isolated homonuclear diatomic molecules in selective vibrational superposition states.

PubMed

Korolkov, M V; Manz, J

2007-05-07

The preparation of matrix isolated homonuclear diatomic molecules in a vibrational superposition state c0Phie=1,v=0+cjPhie=1,v=j, with large (|c0|2 approximately 1) plus small contributions (|cj|2<1) of the ground v=0 and specific v=j low excited vibrational eigenstates, respectively, in the electronic ground (e=1) state, and without any net population transfer to electronic excited (e>1) states, is an important challenge; it serves as a prerequisite for coherent spin control. For this purpose, the authors investigate two scenarios of laser pulse control, involving sequential or intrapulse pump- and dump-type transitions via excited vibronic states Phiex,k with a dominant singlet or triplet character. The mechanisms are demonstrated by means of quantum simulations for representative nuclear wave packets on coupled potential energy surfaces, using as an example a one-dimensional model for Cl2 in an Ar matrix. A simple three-state model (including Phi1,0, Phi1,j and Phiex,k) allows illuminating analyses and efficient determinations of the parameters of the laser pulses based on the values of the transition energies and dipole couplings of the transient state which are derived from the absorption spectra.

The Failure of Eco-Efficiency to Guarantee Sustainability: Future Challenges for Industrial Ecology

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

Huesemann, Michael H.

Western industrialized societies are inherently unsustainable in their present form because they depend almost exclusively on a finite supply of non-renewable minerals and fossil fuels. In addition, the resulting wastes cause various environmental problems ranging from widespread ecosystem disruptions to global warming. The most common response to these problems has been to promote technological improvements in eco-efficiency, which may be defined as ''adding maximum value with minimum resource use and minimum pollution'' (Welford 1997). While constructive, improvements in eco-efficiency alone will not guarantee sustainability of industrialized societies because the limited supplies of non-renewable minerals cannot be extended indefinitely via recyclingmore » and substitution, and a transition to renewable and nuclear energy sources would result in significant negative environmental impacts, particularly if deployed on a large scale. In addition, according to the second law of thermodynamics, industrial production technologies have inherently unavoidable environmental impacts. Finally, any hard won improvements in eco-efficiency will soon be negated if growth in population and consumption is allowed to continue. Consequently, long-term industrial sustainability can only be achieved through a transition to a steady-state economy where the total throughput of matter-energy is kept at a constant and sustainable level. This requires not only improvements in eco-efficiency but also a reassessment of fundamental societal values that erroneously equate material consumption and economic growth with well-being and happiness.« less

DNA-Binding Kinetics Determines the Mechanism of Noise-Induced Switching in Gene Networks

PubMed Central

Tse, Margaret J.; Chu, Brian K.; Roy, Mahua; Read, Elizabeth L.

2015-01-01

Gene regulatory networks are multistable dynamical systems in which attractor states represent cell phenotypes. Spontaneous, noise-induced transitions between these states are thought to underlie critical cellular processes, including cell developmental fate decisions, phenotypic plasticity in fluctuating environments, and carcinogenesis. As such, there is increasing interest in the development of theoretical and computational approaches that can shed light on the dynamics of these stochastic state transitions in multistable gene networks. We applied a numerical rare-event sampling algorithm to study transition paths of spontaneous noise-induced switching for a ubiquitous gene regulatory network motif, the bistable toggle switch, in which two mutually repressive genes compete for dominant expression. We find that the method can efficiently uncover detailed switching mechanisms that involve fluctuations both in occupancies of DNA regulatory sites and copy numbers of protein products. In addition, we show that the rate parameters governing binding and unbinding of regulatory proteins to DNA strongly influence the switching mechanism. In a regime of slow DNA-binding/unbinding kinetics, spontaneous switching occurs relatively frequently and is driven primarily by fluctuations in DNA-site occupancies. In contrast, in a regime of fast DNA-binding/unbinding kinetics, switching occurs rarely and is driven by fluctuations in levels of expressed protein. Our results demonstrate how spontaneous cell phenotype transitions involve collective behavior of both regulatory proteins and DNA. Computational approaches capable of simulating dynamics over many system variables are thus well suited to exploring dynamic mechanisms in gene networks. PMID:26488666

Low-temperature high-density magneto-optical trapping of potassium using the open 4S{yields}5P transition at 405 nm

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

McKay, D. C.; Jervis, D.; Fine, D. J.

2011-12-15

We report the laser cooling and trapping of neutral potassium on an open transition. Fermionic {sup 40}K is captured using a magneto-optical trap (MOT) on the closed 4S{sub 1/2}{yields}4P{sub 3/2} transition at 767 nm and then transferred, with high efficiency, to a MOT on the open 4S{sub 1/2}{yields}5P{sub 3/2} transition at 405 nm. Because the 5P{sub 3/2} state has a smaller linewidth than the 4P{sub 3/2} state, the Doppler limit is reduced from 145 {mu}K to 24 {mu}K, and we observe temperatures as low as 63(6) {mu}K. The density of trapped atoms also increases, due to reduced temperature and reducedmore » expulsive light forces. We measure a two-body loss coefficient of {beta}=1.4(1)x10{sup -10} cm{sup 3}/s near saturation intensity, and estimate an upper bound of 8x10{sup -18} cm{sup 2} for the ionization cross section of the 5P state at 405 nm. The combined temperature and density improvement in the 405 nm MOT is a twenty-fold increase in phase-space density over our 767 nm MOT, showing enhanced precooling for quantum gas experiments. A qualitatively similar enhancement is observed in a 405 nm MOT of bosonic {sup 41}K.« less

State-and-transition models: Conceptual versus simulation perspectives, usefulness and breadth of use, and land management applications

USGS Publications Warehouse

Provencher, Louis; Frid, Leonardo; Czembor, Christina; Morisette, Jeffrey T.

2016-01-01

State-and-Transition Simulation Modeling (STSM) is a quantitative analysis method that can consolidate a wide array of resource management issues under a “what-if” scenario exercise. STSM can be seen as an ensemble of models, such as climate models, ecological models, and economic models that incorporate human dimensions and management options. This chapter presents STSM as a tool to help synthesize information on social–ecological systems and to investigate some of the management issues associated with exotic annual Bromus species, which have been described elsewhere in this book. Definitions, terminology, and perspectives on conceptual and computer-simulated stochastic state-and-transition models are given first, followed by a brief review of past STSM studies relevant to the management of Bromus species. A detailed case study illustrates the usefulness of STSM for land management. As a whole, this chapter is intended to demonstrate how STSM can help both managers and scientists: (a) determine efficient resource allocation for monitoring nonnative grasses; (b) evaluate sources of uncertainty in model simulation results involving expert opinion, and their consequences for management decisions; and (c) provide insight into the consequences of predicted local climate change effects on ecological systems invaded by exotic annual Bromus species.

The electronic and transport properties of monolayer transition metal dichalcogenides: a complex band structure analysis

NASA Astrophysics Data System (ADS)

Szczesniak, Dominik

Recently, monolayer transition metal dichalcogenides have attracted much attention due to their potential use in both nano- and opto-electronics. In such applications, the electronic and transport properties of group-VIB transition metal dichalcogenides (MX2 , where M=Mo, W; X=S, Se, Te) are particularly important. Herein, new insight into these properties is presented by studying the complex band structures (CBS's) of MX2 monolayers while accounting for spin-orbit coupling effects. By using the symmetry-based tight-binding model a nonlinear generalized eigenvalue problem for CBS's is obtained. An efficient method for solving such class of problems is presented and gives a complete set of physically relevant solutions. Next, these solutions are characterized and classified into propagating and evanescent states, where the latter states present not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gaps, which describe the tunneling currents in the MX2 materials. The importance of CBS's and tunneling currents is demonstrated by the analysis of the quantum transport across MX2 monolayers within phase field matching theory. Present work has been prepared within the Qatar Energy and Environment Research Institute (QEERI) grand challenge ATHLOC project (Project No. QEERI- GC-3008).

Monitoring with Data Automata

NASA Technical Reports Server (NTRS)

Havelund, Klaus

2014-01-01

We present a form of automaton, referred to as data automata, suited for monitoring sequences of data-carrying events, for example emitted by an executing software system. This form of automata allows states to be parameterized with data, forming named records, which are stored in an efficiently indexed data structure, a form of database. This very explicit approach differs from other automaton-based monitoring approaches. Data automata are also characterized by allowing transition conditions to refer to other parameterized states, and by allowing transitions sequences. The presented automaton concept is inspired by rule-based systems, especially the Rete algorithm, which is one of the well-established algorithms for executing rule-based systems. We present an optimized external DSL for data automata, as well as a comparable unoptimized internal DSL (API) in the Scala programming language, in order to compare the two solutions. An evaluation compares these two solutions to several other monitoring systems.

Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension.

PubMed

Greene, Samuel M; Shan, Xiao; Clary, David C

2016-06-28

Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.

Modeling Temporal Behavior in Large Networks: A Dynamic Mixed-Membership Model

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

Rossi, R; Gallagher, B; Neville, J

Given a large time-evolving network, how can we model and characterize the temporal behaviors of individual nodes (and network states)? How can we model the behavioral transition patterns of nodes? We propose a temporal behavior model that captures the 'roles' of nodes in the graph and how they evolve over time. The proposed dynamic behavioral mixed-membership model (DBMM) is scalable, fully automatic (no user-defined parameters), non-parametric/data-driven (no specific functional form or parameterization), interpretable (identifies explainable patterns), and flexible (applicable to dynamic and streaming networks). Moreover, the interpretable behavioral roles are generalizable, computationally efficient, and natively supports attributes. We applied ourmore » model for (a) identifying patterns and trends of nodes and network states based on the temporal behavior, (b) predicting future structural changes, and (c) detecting unusual temporal behavior transitions. We use eight large real-world datasets from different time-evolving settings (dynamic and streaming). In particular, we model the evolving mixed-memberships and the corresponding behavioral transitions of Twitter, Facebook, IP-Traces, Email (University), Internet AS, Enron, Reality, and IMDB. The experiments demonstrate the scalability, flexibility, and effectiveness of our model for identifying interesting patterns, detecting unusual structural transitions, and predicting the future structural changes of the network and individual nodes.« less

Magnetic field enhancement of organic photovoltaic cells performance.

PubMed

Oviedo-Casado, S; Urbina, A; Prior, J

2017-06-27

Charge separation is a critical process for achieving high efficiencies in organic photovoltaic cells. The initial tightly bound excitonic electron-hole pair has to dissociate fast enough in order to avoid photocurrent generation and thus power conversion efficiency loss via geminate recombination. Such process takes place assisted by transitional states that lie between the initial exciton and the free charge state. Due to spin conservation rules these intermediate charge transfer states typically have singlet character. Here we propose a donor-acceptor model for a generic organic photovoltaic cell in which the process of charge separation is modulated by a magnetic field which tunes the energy levels. The impact of a magnetic field is to intensify the generation of charge transfer states with triplet character via inter-system crossing. As the ground state of the system has singlet character, triplet states are recombination-protected, thus leading to a higher probability of successful charge separation. Using the open quantum systems formalism we demonstrate that the population of triplet charge transfer states grows in the presence of a magnetic field, and discuss the impact on carrier population and hence photocurrent, highlighting its potential as a tool for research on charge transfer kinetics in this complex systems.

The development of tool use: Planning for end-state comfort

PubMed Central

Comalli, David M.; Keen, Rachel; Abraham, Evelyn S.; Foo, Victoria J.; Lee, Mei-Hua; Adolph, Karen E.

2016-01-01

Some grips on the handle of a tool can be planned based on information directly available in the scene. Other grips, however, must be planned based on the final position of the hand. “End-state comfort” grips require an awkward or uncomfortable initial grip so as to later implement the action comfortably and efficiently. From a cognitive perspective, planning for end-state comfort requires a consistent representation of the entire action sequence, including the latter part, which is not based on information directly available in the scene. Many investigators have found that young children fail to demonstrate planning for end-state comfort and that adult-like performance does not appear until about 12 years of age. In two experiments, we used a hammering task that engaged children in a goal-directed action with multiple steps. We assessed end-state-comfort planning in novel ways by measuring children’s hand choice, grip choice, and tool implementation over multiple trials. The hammering task also uniquely allowed us to assess the efficiency of implementation. We replicated the previous developmental trend in 4-, 8-, and 12-year-old children with our novel task. Most important, our data revealed that 4-year-olds are in a transitional stage with several competing strategies exhibited during a single session. Preschoolers changed their grip within trials and across trials, indicating awareness of errors and a willingness to sacrifice speed for more efficient implementation. The end-state-comfort grip initially competes as one grip type among many, but gradually displaces all others. Children’s sensitivity to and drive for efficiency may motivate this change. PMID:27786531

Circularly polarized zero-phonon transitions of vacancies in diamond at high magnetic fields

NASA Astrophysics Data System (ADS)

Braukmann, D.; Glaser, E. R.; Kennedy, T. A.; Bayer, M.; Debus, J.

2018-05-01

We study the circularly polarized photoluminescence of negatively charged (NV-) and neutral (NV0) nitrogen-vacancy ensembles and neutral vacancies (V0) in diamond crystals exposed to magnetic fields of up to 10 T. We determine the orbital and spin Zeeman splitting as well as the energetic ordering of their ground and first-excited states. The spin-triplet and -singlet states of the NV- are described by an orbital Zeeman splitting of about 9 μ eV /T , which corresponds to a positive orbital g -factor of gL=0.164 under application of the magnetic field along the (001) and (111) crystallographic directions, respectively. The zero-phonon line (ZPL) of the NV- singlet is defined as a transition from the 1E' states, which are split by gLμBB , to the 1A1 state. The energies of the zero-phonon triplet transitions show a quadratic dependence on intermediate magnetic field strengths, which we attribute to a mixing of excited states with nonzero orbital angular momentum. Moreover, we identify slightly different spin Zeeman splittings in the ground (gs) and excited (es) triplet states, which can be expressed by a deviation between their spin g -factors: gS ,es=gS ,gs+Δ g with values of Δ g =0.014 and 0.029 in the (001) and (111) geometries, respectively. The degree of circular polarization of the NV- ZPLs depends significantly on the temperature, which is explained by an efficient spin-orbit coupling of the excited states mediated through acoustic phonons. We further demonstrate that the sign of the circular polarization degree is switched under rotation of the diamond crystal. A weak Zeeman splitting similar to Δ g μBB measured for the NV- ZPLs is also obtained for the NV0 zero-phonon lines, from which we conclude that the ground state is composed of two optically active states with compensated orbital contributions and opposite spin-1/2 momentum projections. The zero-phonon lines of the V0 show Zeeman splittings and degrees of the circular polarization with opposite signs. The magnetophotoluminescence data indicate that the electron transition from the T12 states to the 1A ground state defines the zero-phonon emission at 1.674 eV, while the T12→1E transition is responsible for the zero-phonon line at 1.666 eV. The T12 (1E ) states are characterized by an orbital Zeeman splitting with gL=0.071 (0.128).

Molecular symmetry determines the mechanism of a very efficient ultrafast excitation-to-heat conversion in Ni-substituted chlorophylls.

PubMed

Pilch, Mariusz; Dudkowiak, Alina; Jurzyk, Barbara; Lukasiewicz, Jędrzej; Susz, Anna; Stochel, Grażyna; Fiedor, Leszek

2013-01-01

In the Ni-substituted chlorophylls, an ultrafast (<60 fs) deactivation channel is created, which is not present in Ni-porphyrins. This observation prompted us to investigate in detail the mechanism of excitation-to-heat conversion in Ni-substituted chlorophylls, experimentally, using time-resolved laser-induced optoacoustic spectroscopy, and theoretically, using group theory approach. The Ni-substituted chlorophylls show exceptional photostability and the optoacoustic measurements confirm the prompt and very efficient (100%) excitation-into-heat conversion in these complexes. Considering their excellent spectral properties and the loss-free excitation-into-heat conversion they are likely to become a new class of versatile photocalorimetric references. The curious features of the Ni-substituted chlorophylls originate from the symmetry of a ligand field created in the central cavity. The central N-Ni(2+) bonds, formed via the donation of two electrons from each of the sp(2) orbitals of two central nitrogens to an empty [Formula: see text] hybrid centered on Ni(2+), have a considerable covalent character. The extreme rate of excited state relaxation is then not due to a ladder of the metal centered d-states, often invoked in metalloporphyrins, but seems to result from a peculiar topology of the potential energy surface (a saddle-shaped crossing) due to the covalent character of the N-Ni(2+) bonds. This is confirmed by a strong 0→0 character of electronic transitions in these complexes indicating a similarity of their equilibrium geometries in the ground (S(0)) and the excited states (both Q(X) and Q(Y)). The excitation energy is very efficiently converted into molecular vibrations and dissipated as heat, involving the central Ni(2+). These Ni-substituted pigments pose a fine exemplification of symmetry control over properties of excited states of transition metal complexes. Copyright © 2012. Published by Elsevier B.V.

DNA polymerase catalysis in the absence of Watson-Crick hydrogen bonds

PubMed Central

Potapova, Olga; Chan, Chikio; DeLucia, Angela M.; Helquist, Sandra A.; Kool, Eric T.; Grindley, Nigel D. F.; Joyce, Catherine M.

2008-01-01

We report the first pre-steady-state kinetic studies of DNA replication in the absence of hydrogen bonds. We have used nonpolar nucleotide analogues that mimic the shape of a Watson-Crick base pair in order to investigate the kinetic consequences of a lack of hydrogen bonds in the polymerase reaction catalyzed by the Klenow fragment of DNA Polymerase I from Escherichia coli. With a thymine isostere lacking hydrogen bonding ability in the nascent pair, the efficiency (kpol/Kd) of the polymerase reaction is decreased by 30-fold, affecting ground state (Kd) and transition state (kpol) approximately equally. When both thymine and adenine analogues in the nascent pair lack hydrogen bonding ability, the efficiency of the polymerase reaction is decreased by about 1000-fold, with most the decrease attributable to the transition state. Reactions using nonpolar analogues at the primer terminal base pair demonstrated the requirement for a hydrogen bond between the polymerase and the minor groove of the primer-terminal base. The R668A mutation of Klenow fragment abolished this requirement, identifying R668 as the probable hydrogen bond donor. Detailed examination of the kinetic data suggested that Klenow fragment has an extremely low tolerance of even minor deviations of the analogue base pairs from ideal Watson-Crick geometry. Consistent with this idea, some analogue pairings were better tolerated by Klenow fragment mutants having more spacious active sites. By contrast, the Y-family polymerase Dbh was much less sensitive to changes in base pair dimensions, and more dependent on hydrogen bonding between base-paired partners. PMID:16411765

No evidence for an epidemiological transition in sleep patterns among children: a 12-country study.

PubMed

Manyanga, Taru; Barnes, Joel D; Tremblay, Mark S; Katzmarzyk, Peter T; Broyles, Stephanie T; Barreira, Tiago V; Fogelholm, Mikael; Hu, Gang; Maher, Carol; Maia, Jose; Olds, Timothy; Sarmiento, Olga L; Standage, Martyn; Tudor-Locke, Catrine; Chaput, Jean-Philippe

2018-02-01

To examine the relationships between socioeconomic status (SES; household income and parental education) and objectively measured sleep patterns (sleep duration, sleep efficiency, and bedtime) among children from around the world and explore how the relationships differ across country levels of human development. Multinational, cross-sectional study from sites in Australia, Brazil, Canada, China, Colombia, Finland, India, Kenya, Portugal, South Africa, the United Kingdom, and the United States. The International Study of Childhood Obesity, Lifestyle and the Environment. A total of 6040 children aged 9-11 years. Sleep duration, sleep efficiency, and bedtime were monitored over 7 consecutive days using waist-worn accelerometers. Multilevel models were used to examine the relationships between sleep patterns and SES. In country-specific analyses, there were no significant linear trends for sleep duration and sleep efficiency based on income and education levels. There were significant linear trends in 4 countries for bedtime (Australia, United States, United Kingdom, and India), generally showing that children in the lowest income group had later bedtimes. Later bedtimes were associated with lowest level of parental education in only 2 countries (United Kingdom and India). Patterns of associations between sleep characteristics and SES were not different between boys and girls. Sleep patterns of children (especially sleep duration and efficiency) appear unrelated to SES in each of the 12 countries, with no differences across country levels of human development. The lack of evidence for an epidemiological transition in sleep patterns suggests that efforts to improve sleep hygiene of children should not be limited to any specific SES level. Copyright © 2017 National Sleep Foundation. Published by Elsevier Inc. All rights reserved.

A single Markov-type kinetic model accounting for the macroscopic currents of all human voltage-gated sodium channel isoforms.

PubMed

Balbi, Pietro; Massobrio, Paolo; Hellgren Kotaleski, Jeanette

2017-09-01

Modelling ionic channels represents a fundamental step towards developing biologically detailed neuron models. Until recently, the voltage-gated ion channels have been mainly modelled according to the formalism introduced by the seminal works of Hodgkin and Huxley (HH). However, following the continuing achievements in the biophysical and molecular comprehension of these pore-forming transmembrane proteins, the HH formalism turned out to carry limitations and inconsistencies in reproducing the ion-channels electrophysiological behaviour. At the same time, Markov-type kinetic models have been increasingly proven to successfully replicate both the electrophysiological and biophysical features of different ion channels. However, in order to model even the finest non-conducting molecular conformational change, they are often equipped with a considerable number of states and related transitions, which make them computationally heavy and less suitable for implementation in conductance-based neurons and large networks of those. In this purely modelling study we develop a Markov-type kinetic model for all human voltage-gated sodium channels (VGSCs). The model framework is detailed, unifying (i.e., it accounts for all ion-channel isoforms) and computationally efficient (i.e. with a minimal set of states and transitions). The electrophysiological data to be modelled are gathered from previously published studies on whole-cell patch-clamp experiments in mammalian cell lines heterologously expressing the human VGSC subtypes (from NaV1.1 to NaV1.9). By adopting a minimum sequence of states, and using the same state diagram for all the distinct isoforms, the model ensures the lightest computational load when used in neuron models and neural networks of increasing complexity. The transitions between the states are described by original ordinary differential equations, which represent the rate of the state transitions as a function of voltage (i.e., membrane potential). The kinetic model, developed in the NEURON simulation environment, appears to be the simplest and most parsimonious way for a detailed phenomenological description of the human VGSCs electrophysiological behaviour.

Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

PubMed

Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui

2016-03-23

C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

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

Cadiz, Fabian, E-mail: cadiz@insa-toulouse.fr; Tricard, Simon; Gay, Maxime

Developments in optoelectronics and spin-optronics based on transition metal dichalcogenide monolayers (MLs) need materials with efficient optical emission and well-defined transition energies. In as-exfoliated MoS{sub 2} MLs, the photoluminescence (PL) spectra even at low temperature consist typically of broad, overlapping contributions from neutral, charged excitons (trions) and localized states. Here, we show that in superacid treated MoS{sub 2} MLs, the PL intensity increases by up to 60 times at room temperature. The neutral and charged exciton transitions are spectrally well separated in PL and reflectivity at T = 4 K, with linewidth for the neutral exciton of 15 meV, but both transitions have similarmore » intensities compared to the ones in as-exfoliated MLs at the same temperature. Time resolved experiments uncover picoseconds recombination dynamics analyzed separately for charged and neutral exciton emissions. Using the chiral interband selection rules, we demonstrate optically induced valley polarization for both complexes and valley coherence for only the neutral exciton.« less

Transition properties from the Hermitian formulation of the coupled cluster polarization propagator

NASA Astrophysics Data System (ADS)

Tucholska, Aleksandra M.; Modrzejewski, Marcin; Moszynski, Robert

2014-09-01

Theory of one-electron transition density matrices has been formulated within the time-independent coupled cluster method for the polarization propagator [R. Moszynski, P. S. Żuchowski, and B. Jeziorski, Coll. Czech. Chem. Commun. 70, 1109 (2005)]. Working expressions have been obtained and implemented with the coupled cluster method limited to single, double, and linear triple excitations (CC3). Selected dipole and quadrupole transition probabilities of the alkali earth atoms, computed with the new transition density matrices are compared to the experimental data. Good agreement between theory and experiment is found. The results obtained with the new approach are of the same quality as the results obtained with the linear response coupled cluster theory. The one-electron density matrices for the ground state in the CC3 approximation have also been implemented. The dipole moments for a few representative diatomic molecules have been computed with several variants of the new approach, and the results are discussed to choose the approximation with the best balance between the accuracy and computational efficiency.

Light valve based on nonimaging optics with potential application in cold climate greenhouses

NASA Astrophysics Data System (ADS)

Valerio, Angel A.; Mossman, Michele A.; Whitehead, Lorne A.

2014-09-01

We have evaluated a new concept for a variable light valve and thermal insulation system based on nonimaging optics. The system incorporates compound parabolic concentrators and can readily be switched between an open highly light transmissive state and a closed highly thermally insulating state. This variable light valve makes the transition between high thermal insulation and efficient light transmittance practical and may be useful in plant growth environments to provide both adequate sunlight illumination and thermal insulation as needed. We have measured light transmittance values exceeding 80% for the light valve design and achieved thermal insulation values substantially exceeding those of traditional energy efficient windows. The light valve system presented in this paper represents a potential solution for greenhouse food production in locations where greenhouses are not feasible economically due to high heating cost.

Theoretical restrictions on longest implicit time scales in Markov state models of biomolecular dynamics

NASA Astrophysics Data System (ADS)

Sinitskiy, Anton V.; Pande, Vijay S.

2018-01-01

Markov state models (MSMs) have been widely used to analyze computer simulations of various biomolecular systems. They can capture conformational transitions much slower than an average or maximal length of a single molecular dynamics (MD) trajectory from the set of trajectories used to build the MSM. A rule of thumb claiming that the slowest implicit time scale captured by an MSM should be comparable by the order of magnitude to the aggregate duration of all MD trajectories used to build this MSM has been known in the field. However, this rule has never been formally proved. In this work, we present analytical results for the slowest time scale in several types of MSMs, supporting the above rule. We conclude that the slowest implicit time scale equals the product of the aggregate sampling and four factors that quantify: (1) how much statistics on the conformational transitions corresponding to the longest implicit time scale is available, (2) how good the sampling of the destination Markov state is, (3) the gain in statistics from using a sliding window for counting transitions between Markov states, and (4) a bias in the estimate of the implicit time scale arising from finite sampling of the conformational transitions. We demonstrate that in many practically important cases all these four factors are on the order of unity, and we analyze possible scenarios that could lead to their significant deviation from unity. Overall, we provide for the first time analytical results on the slowest time scales captured by MSMs. These results can guide further practical applications of MSMs to biomolecular dynamics and allow for higher computational efficiency of simulations.

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.

Variationally Optimized Free-Energy Flooding for Rate Calculation.

PubMed

McCarty, James; Valsson, Omar; Tiwary, Pratyush; Parrinello, Michele

2015-08-14

We propose a new method to obtain kinetic properties of infrequent events from molecular dynamics simulation. The procedure employs a recently introduced variational approach [Valsson and Parrinello, Phys. Rev. Lett. 113, 090601 (2014)] to construct a bias potential as a function of several collective variables that is designed to flood the associated free energy surface up to a predefined level. The resulting bias potential effectively accelerates transitions between metastable free energy minima while ensuring bias-free transition states, thus allowing accurate kinetic rates to be obtained. We test the method on a few illustrative systems for which we obtain an order of magnitude improvement in efficiency relative to previous approaches and several orders of magnitude relative to unbiased molecular dynamics. We expect an even larger improvement in more complex systems. This and the ability of the variational approach to deal efficiently with a large number of collective variables will greatly enhance the scope of these calculations. This work is a vindication of the potential that the variational principle has if applied in innovative ways.

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

NASA Astrophysics Data System (ADS)

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J.; He, Ran; Bao, Jiming; Goddard, William A., III; Chen, Shuo; Ren, Zhifeng

2016-09-01

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

Transition metal ferrocenyl dithiocarbamates functionalized dye-sensitized solar cells with hydroxy as an anchoring group

NASA Astrophysics Data System (ADS)

Yadav, Reena; Waghadkar, Yogesh; Kociok-Köhn, Gabriele; Kumar, Abhinav; Rane, Sunit B.; Chauhan, Ratna

2016-12-01

Three new transition-metal dithiocarbamates involving ferrocene (Fc), namely [Co(FcCH2EtOHdtc)3] (Co), [M(FcCH2EtOHdtc)2] M = Ni (Ni), Cu (Cu) (EtOHdtc = N-ethanol dithiocarbamate), have been synthesized and characterized by microanalyses, FTIR, 1H and 13C NMR spectroscopies and single crystal X-ray diffraction technique. The peak broadening in the 1H spectrum of the copper complex indicates the paramagnetic behavior of this compound. The observed single quasi-reversible cyclic voltammograms for the complexes indicate the stabilization of a metal center (except copper) other than Fe in their characteristic oxidation state. These complexes have been used as photo-sensitizer in dye-sensitized solar cells which indicates that Co displays the best photosensitization property with an overall conversion efficiency of 3.25 ± 0.04%. The low cell efficiency of Ni and Cu complexes may be due to slow regeneration of the dye by iodine/iodide redox couple followed by charge injection into TiO2.

Renormalization group approach to symmetry protected topological phases

NASA Astrophysics Data System (ADS)

van Nieuwenburg, Evert P. L.; Schnyder, Andreas P.; Chen, Wei

2018-04-01

A defining feature of a symmetry protected topological phase (SPT) in one dimension is the degeneracy of the Schmidt values for any given bipartition. For the system to go through a topological phase transition separating two SPTs, the Schmidt values must either split or cross at the critical point in order to change their degeneracies. A renormalization group (RG) approach based on this splitting or crossing is proposed, through which we obtain an RG flow that identifies the topological phase transitions in the parameter space. Our approach can be implemented numerically in an efficient manner, for example, using the matrix product state formalism, since only the largest first few Schmidt values need to be calculated with sufficient accuracy. Using several concrete models, we demonstrate that the critical points and fixed points of the RG flow coincide with the maxima and minima of the entanglement entropy, respectively, and the method can serve as a numerically efficient tool to analyze interacting SPTs in the parameter space.

Choreographing an enzyme’s dance

PubMed Central

Villali, Janice; Kern, Dorothee

2010-01-01

While ground state structures combined with chemical tools and enzyme kinetics deliver useful information on possible chemical mechanisms of enzyme catalysis, they do not unravel the finely balanced energy inventory to explain the impressive rate enhancement of enzymes. For this goal, a complete description of enzyme catalysis in the form of an energy landscape is needed. Since the rate of catalysis is determined by the climb over a sequence of energy barriers, we focus here on the critical question of transition pathways. A combination of time-resolved NMR and simulation deliver a glimpse into how proteins can so efficiently move within the ensemble of the native conformations while avoiding unfolding during that journey. The loss of energy due to breakage of native contacts is compensated by non-native transient hydrogen bonds during the transition thereby “holding on” to the energy until the new native contacts form that define the alternate functional state. The use of kinetic isotope effects (KIE) to study the chemical step show that coordinated atomic fluctuations of the protein component dictate the probability of “correct” distance and orientation, due to its extreme sensitivity to distance. The examples here stress the point that highly choreographed conformational sampling together with chemical integrity is a prerequisite for efficient enzyme catalysis. PMID:20822946

Precision measurement of ^23Al beta-decay

NASA Astrophysics Data System (ADS)

Zhai, Yongjun; Iacob, V. E.; Hardy, J. C.; Al-Abdullah, T.; Banu, A.; Fu, C.; Golovko, V. V.; McCleskey, M.; Nica, N.; Park, H. I.; Tabacaru, G.; Tribble, R. E.; Trache, L.

2007-10-01

The beta-decay of ^23Al (See [1]) was re-measured with higher statistics and better accuracy at Texas A&M University. Using MARS we produced and separated pure ^23Al at 4000 pps, with a 48 MeV/u ^24Mg beam via the ^24Mg (p, 2n)^ 23Al reaction on a H2 cryogenic target. New β and β-γ coincidence measurements were made with a scintillator, an HPGe detector with BGO shielding and the fast tape transport system. The BGO Compton shield very much improved the quality of the γ spectra around the transition from the IAS state at 7803 keV. From the measured β singles and β-γ coincidence decay spectra we obtained an improved β-decay scheme and a more precise lifetime: t=447(4) ms. We use the method of detailed balance to obtain absolute β-branching ratios and absolute logft values for transitions to final states in ^23Mg. For this method, precise efficiency calibration of the HPGe detector up to about 8 MeV is needed. We extended our previous efficiency calibration to the range Eγ=3.5-8 MeV using the β-decay of ^24Al. [1] V.E. Iacob, Y. Zhai et al., Phys. Rev. C 74, 045810 (2006).

Role of Chemical Reactivity and Transition State Modeling for Virtual Screening.

PubMed

Karthikeyan, Muthukumarasamy; Vyas, Renu; Tambe, Sanjeev S; Radhamohan, Deepthi; Kulkarni, Bhaskar D

2015-01-01

Every drug discovery research program involves synthesis of a novel and potential drug molecule utilizing atom efficient, economical and environment friendly synthetic strategies. The current work focuses on the role of the reactivity based fingerprints of compounds as filters for virtual screening using a tool ChemScore. A reactant-like (RLS) and a product- like (PLS) score can be predicted for a given compound using the binary fingerprints derived from the numerous known organic reactions which capture the molecule-molecule interactions in the form of addition, substitution, rearrangement, elimination and isomerization reactions. The reaction fingerprints were applied to large databases in biology and chemistry, namely ChEMBL, KEGG, HMDB, DSSTox, and the Drug Bank database. A large network of 1113 synthetic reactions was constructed to visualize and ascertain the reactant product mappings in the chemical reaction space. The cumulative reaction fingerprints were computed for 4000 molecules belonging to 29 therapeutic classes of compounds, and these were found capable of discriminating between the cognition disorder related and anti-allergy compounds with reasonable accuracy of 75% and AUC 0.8. In this study, the transition state based fingerprints were also developed and used effectively for virtual screening in drug related databases. The methodology presented here provides an efficient handle for the rapid scoring of molecular libraries for virtual screening.

Fuel Cell Buses in U.S. Transit Fleets: Current Status 2016

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

Eudy, Leslie; Post, Matthew; Jeffers, Matthew

This report, published annually, summarizes the progress of fuel cell electric bus development in the United States and discusses the achievements and challenges of introducing fuel cell propulsion in transit. The report provides a summary of results from evaluations performed by the National Renewable Energy Laboratory. Funding for this effort is provided by the U.S. Department of Energy's Fuel Cell Technologies Office within the Office of Energy Efficiency and Renewable Energy and by the U.S. Department of Transportation's Federal Transit Administration. The 2016 summary results primarily focus on the most recent year for each demonstration, from August 2015 through Julymore » 2016. The results for these buses account for more than 550,000 miles traveled and 59,500 hours of fuel cell power system operation. The primary results presented in the report are from three demonstrations of two different fuel-cell-dominant bus designs: Zero Emission Bay Area Demonstration Group led by Alameda-Contra Costa Transit District (AC Transit) in California; American Fuel Cell Bus Project at SunLine Transit Agency in California; and American Fuel Cell Bus Project at the University of California at Irvine.« less

Minimum Free Energy Path of Ligand-Induced Transition in Adenylate Kinase

PubMed Central

Matsunaga, Yasuhiro; Fujisaki, Hiroshi; Terada, Tohru; Furuta, Tadaomi; Moritsugu, Kei; Kidera, Akinori

2012-01-01

Large-scale conformational changes in proteins involve barrier-crossing transitions on the complex free energy surfaces of high-dimensional space. Such rare events cannot be efficiently captured by conventional molecular dynamics simulations. Here we show that, by combining the on-the-fly string method and the multi-state Bennett acceptance ratio (MBAR) method, the free energy profile of a conformational transition pathway in Escherichia coli adenylate kinase can be characterized in a high-dimensional space. The minimum free energy paths of the conformational transitions in adenylate kinase were explored by the on-the-fly string method in 20-dimensional space spanned by the 20 largest-amplitude principal modes, and the free energy and various kinds of average physical quantities along the pathways were successfully evaluated by the MBAR method. The influence of ligand binding on the pathways was characterized in terms of rigid-body motions of the lid-shaped ATP-binding domain (LID) and the AMP-binding (AMPbd) domains. It was found that the LID domain was able to partially close without the ligand, while the closure of the AMPbd domain required the ligand binding. The transition state ensemble of the ligand bound form was identified as those structures characterized by highly specific binding of the ligand to the AMPbd domain, and was validated by unrestrained MD simulations. It was also found that complete closure of the LID domain required the dehydration of solvents around the P-loop. These findings suggest that the interplay of the two different types of domain motion is an essential feature in the conformational transition of the enzyme. PMID:22685395

Phase Transitions and Volunteering in Spatial Public Goods Games

NASA Astrophysics Data System (ADS)

Szabó, György; Hauert, Christoph

2002-08-01

We present a simple yet effective mechanism promoting cooperation under full anonymity by allowing for voluntary participation in public goods games. This natural extension leads to ``rock-scissors-paper''-type cyclic dominance of the three strategies, cooperate, defect, and loner. In spatial settings with players arranged on a regular lattice, this results in interesting dynamical properties and intriguing spatiotemporal patterns. In particular, variations of the value of the public good leads to transitions between one-, two-, and three-strategy states which either are in the class of directed percolation or show interesting analogies to Ising-type models. Although volunteering is incapable of stabilizing cooperation, it efficiently prevents successful spreading of selfish behavior.

The Dynamics of Truncated Black Hole Accretion Disks. II. Magnetohydrodynamic Case

NASA Astrophysics Data System (ADS)

Hogg, J. Drew; Reynolds, Christopher S.

2018-02-01

We study a truncated accretion disk using a well-resolved, semi-global magnetohydrodynamic simulation that is evolved for many dynamical times (6096 inner disk orbits). The spectral properties of hard-state black hole binary systems and low-luminosity active galactic nuclei are regularly attributed to truncated accretion disks, but a detailed understanding of the flow dynamics is lacking. In these systems the truncation is expected to arise through thermal instability driven by sharp changes in the radiative efficiency. We emulate this behavior using a simple bistable cooling function with efficient and inefficient branches. The accretion flow takes on an arrangement where a “transition zone” exists in between hot gas in the innermost regions and a cold, Shakura & Sunyaev thin disk at larger radii. The thin disk is embedded in an atmosphere of hot gas that is fed by a gentle outflow originating from the transition zone. Despite the presence of hot gas in the inner disk, accretion is efficient. Our analysis focuses on the details of the angular momentum transport, energetics, and magnetic field properties. We find that the magnetic dynamo is suppressed in the hot, truncated inner region of the disk which lowers the effective α-parameter by 65%.

Subtle Monte Carlo Updates in Dense Molecular Systems.

PubMed

Bottaro, Sandro; Boomsma, Wouter; E Johansson, Kristoffer; Andreetta, Christian; Hamelryck, Thomas; Ferkinghoff-Borg, Jesper

2012-02-14

Although Markov chain Monte Carlo (MC) simulation is a potentially powerful approach for exploring conformational space, it has been unable to compete with molecular dynamics (MD) in the analysis of high density structural states, such as the native state of globular proteins. Here, we introduce a kinetic algorithm, CRISP, that greatly enhances the sampling efficiency in all-atom MC simulations of dense systems. The algorithm is based on an exact analytical solution to the classic chain-closure problem, making it possible to express the interdependencies among degrees of freedom in the molecule as correlations in a multivariate Gaussian distribution. We demonstrate that our method reproduces structural variation in proteins with greater efficiency than current state-of-the-art Monte Carlo methods and has real-time simulation performance on par with molecular dynamics simulations. The presented results suggest our method as a valuable tool in the study of molecules in atomic detail, offering a potential alternative to molecular dynamics for probing long time-scale conformational transitions.

Creation of ultracold molecules within the lifetime scale by direct implementation of an optical frequency comb

NASA Astrophysics Data System (ADS)

Liu, Gengyuan; Malinovskaya, S. A.

2018-06-01

A method is proposed to create molecules in the ultracold state from the Feshbach molecules by stepwise adiabatic passage using an optical frequency comb without losses due to decoherence. An emphasis is made on the impact of the vibrational state manifold on controllability of the coherent dynamics by including five excited states into the model. The results are compared with recently reported results on a three-level ? system. Sinusoidal modulation across an individual pulse in the pulse train is applied, leading to the creation of a quasi-dark state, which minimizes population of the transitional, vibrational state manifold, and efficiently mitigates decoherence in the system. The parity of the temporal chirp is shown to be an important factor in designing population dynamics in the system.

CuTaS 3 : Intermetal d–d Transitions Enable High Solar Absorption

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

Heo, Jaeseok; Yu, Liping; Altschul, Emmeline

To realize the fundamental limits of photovoltaic device efficiency, solar absorbers must exhibit strong absorption and abrupt absorption onsets. Ideally, onsets to maximum absorption (a > 105 cm-1) occur over a few tenths of an electronvolt. First-principles calculations predict CuTaS3 represents a potentially new class of materials with such absorption characteristics. Narrow metallic d bands in both the initial and final states present high joint densities of states and, therefore, strong absorption. Specifically, a mixture of metal d (Cu1+, d10) and S p characterizes states near the valence band maximum, and metal d (Ta5+, d0) dominates near the conduction bandmore » minimum. Optical absorption measurements on thin films confirm the abrupt onset to strong absorption a > 105 cm-1 at Eg + 0.4 eV (Eg = 1.0 eV). Theoretical CuTaS3 solar cell efficiency is predicted to be 28% for a 300 nm film based on the metric of spectroscopic limited maximum efficiency, which exceeds that of CuInSe2. This sulfide may offer new opportunities to discover and develop a new class of mixed d-element solar absorbers.« less

Promises and challenges in solid-state lighting

NASA Astrophysics Data System (ADS)

Schubert, Fred

2010-03-01

Lighting technologies based on semiconductor light-emitting diodes (LEDs) offer unprecedented promises that include three major benefits: (i) Gigantic energy savings enabled by efficient conversion of electrical energy to optical energy; (ii) Substantial positive contributions to sustainability through reduced emissions of global-warming gases, acid-rain gases, and toxic substances such as mercury; and (iii) The creation of new paradigms in lighting driven by the unique controllability of solid-state lighting sources. Due to the powerful nature of these benefits, the transition from conventional lighting sources to solid-state lighting is virtually assured. This presentation will illustrate the new world of lighting and illustrate the pervasive changes to be expected in lighting, displays, communications, and biotechnology. The presentation will also address the formidable challenges that must be addressed to continue the further advancement of solid-state lighting technology. These challenges offer opportunities for research and innovation. Specific challenges include light management, carrier transport, and optical design. We will present some innovative approaches in order to solve known technical challenges faced by solid-state lighting. These approaches include the demonstration and use of new optical thin-film materials with a continuously tunable refractive index. These approaches also include the use of polarization-matched structures that reduce the polarization fields in GaInN LEDs and the hotly debated efficiency droop, that is, the decreasing LED efficiency at high currents.

Using Cryogenics to Improve the Efficiency of Photovoltaic Solar Cells

NASA Astrophysics Data System (ADS)

Somers, Hunter; Martinez, Estefano; Ganley, Grace; Rivera, Daniel; Hopp, Aric; Jakachira, Takunda; West, Andrea; Sapp, Whitley; Watson, Casey R.; Paulin, Pete

Improving the reliability and profitability of green energy sources plays a crucial part in transitioning away from fossil fuels as an energy source. As a possible means of making solar energy production more efficient, we consider the effects of cryogenically treating photovoltaic (PV) solar panels at 300 Below, Inc. We report on the pre- and post-cryo performance of two different types of solar panels, when they are exposed to the same, artificial light source. Then, using NREL data, we project the financial benefits of adopting cryogenically treated solar panels throughout the United States over the next five years. 300 Below Inc.

Tuning direct bandgap GeSn/Ge quantum dots' interband and intraband useful emission wavelength: Towards CMOS compatible infrared optical devices

NASA Astrophysics Data System (ADS)

Baira, Mourad; Salem, Bassem; Madhar, Niyaz Ahamad; Ilahi, Bouraoui

2018-05-01

In this work, interband and intraband optical transitions from direct bandgap strained GeSn/Ge quantum dots are numerically tuned by evaluating the confined energies for heavy holes and electrons in D- and L-valley. The practically exploitable emission wavelength ranges for efficient use in light emission and sensing should fulfill specific criteria imposing the electrons confined states in D-valley to be sufficiently below those in L-valley. This study shows that GeSn quantum dots offer promising opportunity towards high efficient group IV based infrared optical devices operating in the mid-IR and far-IR wavelength regions.

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.

Photon energy upconversion through thermal radiation with the power efficiency reaching 16%.

PubMed

Wang, Junxin; Ming, Tian; Jin, Zhao; Wang, Jianfang; Sun, Ling-Dong; Yan, Chun-Hua

2014-11-28

The efficiency of many solar energy conversion technologies is limited by their poor response to low-energy solar photons. One way for overcoming this limitation is to develop materials and methods that can efficiently convert low-energy photons into high-energy ones. Here we show that thermal radiation is an attractive route for photon energy upconversion, with efficiencies higher than those of state-of-the-art energy transfer upconversion under continuous wave laser excitation. A maximal power upconversion efficiency of 16% is achieved on Yb(3+)-doped ZrO2. By examining various oxide samples doped with lanthanide or transition metal ions, we draw guidelines that materials with high melting points, low thermal conductivities and strong absorption to infrared light deliver high upconversion efficiencies. The feasibility of our upconversion approach is further demonstrated under concentrated sunlight excitation and continuous wave 976-nm laser excitation, where the upconverted white light is absorbed by Si solar cells to generate electricity and drive optical and electrical devices.

High-Fidelity Aerodynamic Shape Optimization for Natural Laminar Flow

NASA Astrophysics Data System (ADS)

Rashad, Ramy

To ensure the long-term sustainability of aviation, serious effort is underway to mitigate the escalating economic, environmental, and social concerns of the industry. Significant improvement to the energy efficiency of air transportation is required through the research and development of advanced and unconventional airframe and engine technologies. In the quest to reduce airframe drag, this thesis is concerned with the development and demonstration of an effective design tool for improving the aerodynamic efficiency of subsonic and transonic airfoils. The objective is to advance the state-of-the-art in high-fidelity aerodynamic shape optimization by incorporating and exploiting the phenomenon of laminar-turbulent transition in an efficient manner. A framework for the design and optimization of Natural Laminar Flow (NLF) airfoils is developed and demonstrated with transition prediction capable of accounting for the effects of Reynolds number, freestream turbulence intensity, Mach number, and pressure gradients. First, a two-dimensional Reynolds-averaged Navier-Stokes (RANS) flow solver has been extended to incorporate an iterative laminar-turbulent transition prediction methodology. The natural transition locations due to Tollmien-Schlichting instabilities are predicted using the simplified eN envelope method of Drela and Giles or, alternatively, the compressible form of the Arnal-Habiballah-Delcourt criterion. The boundary-layer properties are obtained directly from the Navier-Stokes flow solution, and the transition to turbulent flow is modeled using an intermittency function in conjunction with the Spalart-Allmaras turbulence model. The RANS solver is subsequently employed in a gradient-based sequential quadratic programming shape optimization framework. The laminar-turbulent transition criteria are tightly coupled into the objective and gradient evaluations. The gradients are obtained using a new augmented discrete-adjoint formulation for non-local transition criteria. Using the eN transition criterion, the proposed framework is applied to the single and multipoint optimization of subsonic and transonic airfoils, leading to robust NLF designs. The aerodynamic design requirements over a range of cruise flight conditions are cast into a multipoint optimization problem through a composite objective defined using a weighted integral of the operating points. To study and quantify off-design performance, a Pareto front is formed using a weighted objective combining free-transition and fully-turbulent operating conditions. Next we examine the sensitivity of NLF design to the freestream disturbance environment, highlighting the on- and off-design performance at different critical N-factors. Finally, we propose and demonstrate a technique to enable the design of airfoils with robust performance over a range of critical N-factors.

Arbitrary-quantum-state preparation of a harmonic oscillator via optimal control

NASA Astrophysics Data System (ADS)

Rojan, Katharina; Reich, Daniel M.; Dotsenko, Igor; Raimond, Jean-Michel; Koch, Christiane P.; Morigi, Giovanna

2014-08-01

The efficient initialization of a quantum system is a prerequisite for quantum technological applications. Here we show that several classes of quantum states of a harmonic oscillator can be efficiently prepared by means of a Jaynes-Cummings interaction with a single two-level system. This is achieved by suitably tailoring external fields which drive the dipole and/or the oscillator. The time-dependent dynamics that leads to the target state is identified by means of optimal control theory (OCT) based on Krotov's method. Infidelities below 10-4 can be reached for the parameters of the experiment of Raimond, Haroche, Brune and co-workers, where the oscillator is a mode of a high-Q microwave cavity and the dipole is a Rydberg transition of an atom. For this specific situation we analyze the limitations on the fidelity due to parameter fluctuations and identify robust dynamics based on pulses found using ensemble OCT. Our analysis can be extended to quantum-state preparation of continuous-variable systems in other platforms, such as trapped ions and circuit QED.

Revisiting Photoemission and Inverse Photoemission Spectra of Nickel Oxide from First Principles: Implications for Solar Energy Conversion

PubMed Central

2015-01-01

We use two different ab initio quantum mechanics methods, complete active space self-consistent field theory applied to electrostatically embedded clusters and periodic many-body G0W0 calculations, to reanalyze the states formed in nickel(II) oxide upon electron addition and ionization. In agreement with interpretations of earlier measurements, we find that the valence and conduction band edges consist of oxygen and nickel states, respectively. However, contrary to conventional wisdom, we find that the oxygen states of the valence band edge are localized whereas the nickel states at the conduction band edge are delocalized. We argue that these characteristics may lead to low electron–hole recombination and relatively efficient electron transport, which, coupled with band gap engineering, could produce higher solar energy conversion efficiency compared to that of other transition-metal oxides. Both methods find a photoemission/inverse-photoemission gap of 3.6–3.9 eV, in good agreement with the experimental range, lending credence to our analysis of the electronic structure of NiO. PMID:24689856

Incorporating Linear Synchronous Transit Interpolation into the Growing String Method: Algorithm and Applications.

PubMed

Behn, Andrew; Zimmerman, Paul M; Bell, Alexis T; Head-Gordon, Martin

2011-12-13

The growing string method is a powerful tool in the systematic study of chemical reactions with theoretical methods which allows for the rapid identification of transition states connecting known reactant and product structures. However, the efficiency of this method is heavily influenced by the choice of interpolation scheme when adding new nodes to the string during optimization. In particular, the use of Cartesian coordinates with cubic spline interpolation often produces guess structures which are far from the final reaction path and require many optimization steps (and thus many energy and gradient calculations) to yield a reasonable final structure. In this paper, we present a new method for interpolating and reparameterizing nodes within the growing string method using the linear synchronous transit method of Halgren and Lipscomb. When applied to the alanine dipeptide rearrangement and a simplified cationic alkyl ring condensation reaction, a significant speedup in terms of computational cost is achieved (30-50%).

Direct real-time detection of the structural and biochemical events in the myosin power stroke.

PubMed

Muretta, Joseph M; Rohde, John A; Johnsrud, Daniel O; Cornea, Sinziana; Thomas, David D

2015-11-17

A principal goal of molecular biophysics is to show how protein structural transitions explain physiology. We have developed a strategic tool, transient time-resolved FRET [(TR)(2)FRET], for this purpose and use it here to measure directly, with millisecond resolution, the structural and biochemical kinetics of muscle myosin and to determine directly how myosin's power stroke is coupled to the thermodynamic drive for force generation, actin-activated phosphate release, and the weak-to-strong actin-binding transition. We find that actin initiates the power stroke before phosphate dissociation and not after, as many models propose. This result supports a model for muscle contraction in which power output and efficiency are tuned by the distribution of myosin structural states. This technology should have wide application to other systems in which questions about the temporal coupling of allosteric structural and biochemical transitions remain unanswered.

S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering

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

Manthe, Uwe, E-mail: uwe.manthe@uni-bielefeld.de; Ellerbrock, Roman, E-mail: roman.ellerbrock@uni-bielefeld.de

2016-05-28

A new approach for the quantum-state resolved analysis of polyatomic reactions is introduced. Based on the singular value decomposition of the S-matrix, energy-dependent natural reaction channels and natural reaction probabilities are defined. It is shown that the natural reaction probabilities are equal to the eigenvalues of the reaction probability operator [U. Manthe and W. H. Miller, J. Chem. Phys. 99, 3411 (1993)]. Consequently, the natural reaction channels can be interpreted as uniquely defined pathways through the transition state of the reaction. The analysis can efficiently be combined with reactive scattering calculations based on the propagation of thermal flux eigenstates. Inmore » contrast to a decomposition based straightforwardly on thermal flux eigenstates, it does not depend on the choice of the dividing surface separating reactants from products. The new approach is illustrated studying a prototypical example, the H + CH{sub 4} → H{sub 2} + CH{sub 3} reaction. The natural reaction probabilities and the contributions of the different vibrational states of the methyl product to the natural reaction channels are calculated and discussed. The relation between the thermal flux eigenstates and the natural reaction channels is studied in detail.« less

Model-Checking with Edge-Valued Decision Diagrams

NASA Technical Reports Server (NTRS)

Roux, Pierre; Siminiceanu, Radu I.

2010-01-01

We describe an algebra of Edge-Valued Decision Diagrams (EVMDDs) to encode arithmetic functions and its implementation in a model checking library along with state-of-the-art algorithms for building the transition relation and the state space of discrete state systems. We provide efficient algorithms for manipulating EVMDDs and give upper bounds of the theoretical time complexity of these algorithms for all basic arithmetic and relational operators. We also demonstrate that the time complexity of the generic recursive algorithm for applying a binary operator on EVMDDs is no worse than that of Multi-Terminal Decision Diagrams. We have implemented a new symbolic model checker with the intention to represent in one formalism the best techniques available at the moment across a spectrum of existing tools: EVMDDs for encoding arithmetic expressions, identity-reduced MDDs for representing the transition relation, and the saturation algorithm for reachability analysis. We compare our new symbolic model checking EVMDD library with the widely used CUDD package and show that, in many cases, our tool is several orders of magnitude faster than CUDD.

General methods for sensitivity analysis of equilibrium dynamics in patch occupancy models

USGS Publications Warehouse

Miller, David A.W.

2012-01-01

Sensitivity analysis is a useful tool for the study of ecological models that has many potential applications for patch occupancy modeling. Drawing from the rich foundation of existing methods for Markov chain models, I demonstrate new methods for sensitivity analysis of the equilibrium state dynamics of occupancy models. Estimates from three previous studies are used to illustrate the utility of the sensitivity calculations: a joint occupancy model for a prey species, its predators, and habitat used by both; occurrence dynamics from a well-known metapopulation study of three butterfly species; and Golden Eagle occupancy and reproductive dynamics. I show how to deal efficiently with multistate models and how to calculate sensitivities involving derived state variables and lower-level parameters. In addition, I extend methods to incorporate environmental variation by allowing for spatial and temporal variability in transition probabilities. The approach used here is concise and general and can fully account for environmental variability in transition parameters. The methods can be used to improve inferences in occupancy studies by quantifying the effects of underlying parameters, aiding prediction of future system states, and identifying priorities for sampling effort.

Efficient and robust relaxation procedures for multi-component mixtures including phase transition

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

Han, Ee, E-mail: eehan@math.uni-bremen.de; Hantke, Maren, E-mail: maren.hantke@ovgu.de; Müller, Siegfried, E-mail: mueller@igpm.rwth-aachen.de

We consider a thermodynamic consistent multi-component model in multi-dimensions that is a generalization of the classical two-phase flow model of Baer and Nunziato. The exchange of mass, momentum and energy between the phases is described by additional source terms. Typically these terms are handled by relaxation procedures. Available relaxation procedures suffer from efficiency and robustness resulting in very costly computations that in general only allow for one-dimensional computations. Therefore we focus on the development of new efficient and robust numerical methods for relaxation processes. We derive exact procedures to determine mechanical and thermal equilibrium states. Further we introduce a novelmore » iterative method to treat the mass transfer for a three component mixture. All new procedures can be extended to an arbitrary number of inert ideal gases. We prove existence, uniqueness and physical admissibility of the resulting states and convergence of our new procedures. Efficiency and robustness of the procedures are verified by means of numerical computations in one and two space dimensions. - Highlights: • We develop novel relaxation procedures for a generalized, thermodynamically consistent Baer–Nunziato type model. • Exact procedures for mechanical and thermal relaxation procedures avoid artificial parameters. • Existence, uniqueness and physical admissibility of the equilibrium states are proven for special mixtures. • A novel iterative method for mass transfer is introduced for a three component mixture providing a unique and admissible equilibrium state.« less

Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

PubMed

Wang, Hui-Fang; Liu, Zhi-Pan

2008-08-20

Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

Study of chemical reactivity in relation to experimental parameters of efficiency in coumarin derivatives for dye sensitized solar cells using DFT.

PubMed

Soto-Rojo, Rody; Baldenebro-López, Jesús; Glossman-Mitnik, Daniel

2015-06-07

A group of dyes derived from coumarin was studied, which consisted of nine molecules using a very similar manufacturing process of dye sensitized solar cells (DSSCs). Optimized geometries, energy levels of the highest occupied molecular orbital and the lowest unoccupied molecular orbital, and ultraviolet-visible spectra were obtained using theoretical calculations, and they were also compared with experimental conversion efficiencies of the DSSC. The representation of an excited state in terms of natural transition orbitals (NTOs) was studied. Chemical reactivity parameters were calculated and correlated with the experimental data linked to the efficiency of the DSSC. A new proposal was obtained to design new molecular systems and to predict their potential use as a dye in DSSCs.

Synthesis of energy-efficient FSMs implemented in PLD circuits

NASA Astrophysics Data System (ADS)

Nawrot, Radosław; Kulisz, Józef; Kania, Dariusz

2017-11-01

The paper presents an outline of a simple synthesis method of energy-efficient FSMs. The idea consists in using local clock gating to selectively block the clock signal, if no transition of a state of a memory element is required. The research was dedicated to logic circuits using Programmable Logic Devices as the implementation platform, but the conclusions can be applied to any synchronous circuit. The experimental section reports a comparison of three methods of implementing sequential circuits in PLDs with respect to clock distribution: the classical fully synchronous structure, the structure exploiting the Enable Clock inputs of memory elements, and the structure using clock gating. The results show that the approach based on clock gating is the most efficient one, and it leads to significant reduction of dynamic power consumed by the FSM.

Voltage Control of Metal-insulator Transition and Non-volatile Ferroelastic Switching of Resistance in VOx/PMN-PT Heterostructures

PubMed Central

Nan, Tianxiang; Liu, Ming; Ren, Wei; Ye, Zuo-Guang; Sun, Nian X.

2014-01-01

The central challenge in realizing electronics based on strongly correlated electronic states, or ‘Mottronics', lies in finding an energy efficient way to switch between the distinct collective phases with a control voltage in a reversible and reproducible manner. In this work, we demonstrate that a voltage-impulse-induced ferroelastic domain switching in the (011)-oriented 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-PT) substrates allows a robust non-volatile tuning of the metal-insulator transition in the VOx films deposited onto them. In such a VOx/PMN-PT heterostructure, the unique two-step electric polarization switching covers up to 90% of the entire poled area and contributes to a homogeneous in-plane anisotropic biaxial strain, which, in turn, enables the lattice changes and results in the suppression of metal-insulator transition in the mechanically coupled VOx films by 6 K with a resistance change up to 40% over a broad range of temperature. These findings provide a framework for realizing in situ and non-volatile tuning of strain-sensitive order parameters in strongly correlated materials, and demonstrate great potentials in delivering reconfigurable, compactable, and energy-efficient electronic devices. PMID:25088796

Voltage control of metal-insulator transition and non-volatile ferroelastic switching of resistance in VOx/PMN-PT heterostructures.

PubMed

Nan, Tianxiang; Liu, Ming; Ren, Wei; Ye, Zuo-Guang; Sun, Nian X

2014-08-04

The central challenge in realizing electronics based on strongly correlated electronic states, or 'Mottronics', lies in finding an energy efficient way to switch between the distinct collective phases with a control voltage in a reversible and reproducible manner. In this work, we demonstrate that a voltage-impulse-induced ferroelastic domain switching in the (011)-oriented 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-PT) substrates allows a robust non-volatile tuning of the metal-insulator transition in the VOx films deposited onto them. In such a VOx/PMN-PT heterostructure, the unique two-step electric polarization switching covers up to 90% of the entire poled area and contributes to a homogeneous in-plane anisotropic biaxial strain, which, in turn, enables the lattice changes and results in the suppression of metal-insulator transition in the mechanically coupled VOx films by 6 K with a resistance change up to 40% over a broad range of temperature. These findings provide a framework for realizing in situ and non-volatile tuning of strain-sensitive order parameters in strongly correlated materials, and demonstrate great potentials in delivering reconfigurable, compactable, and energy-efficient electronic devices.

Elevated CO2 causes changes in the photosynthetic apparatus of a toxic cyanobacterium, Cylindrospermopsis raciborskii.

PubMed

Pierangelini, Mattia; Stojkovic, Slobodanka; Orr, Philip T; Beardall, John

2014-07-15

We studied the physiological acclimation of growth, photosynthesis and CO2-concentrating mechanism (CCM) in Cylindrospermopsis raciborskii exposed to low (present day; L-CO2) and high (1300ppm; H-CO2) pCO2. Results showed that under H-CO2 the cell specific division rate (μc) was higher and the CO2- and light-saturated photosynthetic rates (Vmax and Pmax) doubled. The cells' photosynthetic affinity for CO2 (K0.5CO2) was halved compared to L-CO2 cultures. However, no significant differences were found in dark respiration rates (Rd), pigment composition and light harvesting efficiency (α). In H-CO2 cells, non-photochemical quenching (NPQ), associated with state transitions of the electron transport chain (ETC), was negligible. Simultaneously, a reorganisation of PSII features including antenna connectivity (JconPSIIα), heterogeneity (PSIIα/β) and effective absorption cross sectional area (σPSIIα/β) was observed. In relation to different activities of the CCM, our findings suggest that for cells grown under H-CO2: (1) there is down-regulation of CCM activity; (2) the ability of cells to use the harvested light energy is altered; (3) the occurrence of state transitions is likely to be associated with changes of electron flow (cyclic vs linear) through the ETC; (4) changes in PSII characteristics are important in regulating state transitions. Copyright © 2014 Elsevier GmbH. All rights reserved.

Data Automata in Scala

NASA Technical Reports Server (NTRS)

Havelund, Klaus

2014-01-01

The field of runtime verification has during the last decade seen a multitude of systems for monitoring event sequences (traces) emitted by a running system. The objective is to ensure correctness of a system by checking its execution traces against formal specifications representing requirements. A special challenge is data parameterized events, where monitors have to keep track of the combination of control states as well as data constraints, relating events and the data they carry across time points. This poses a challenge wrt. efficiency of monitors, as well as expressiveness of logics. Data automata is a form of automata where states are parameterized with data, supporting monitoring of data parameterized events. We describe the full details of a very simple API in the Scala programming language, an internal DSL (Domain-Specific Language), implementing data automata. The small implementation suggests a design pattern. Data automata allow transition conditions to refer to other states than the source state, and allow target states of transitions to be inlined, offering a temporal logic flavored notation. An embedding of a logic in a high-level language like Scala in addition allows monitors to be programmed using all of Scala's language constructs, offering the full flexibility of a programming language. The framework is demonstrated on an XML processing scenario previously addressed in related work.

Steady-state hydrodynamic instabilities of active liquid crystals: hybrid lattice Boltzmann simulations.

PubMed

Marenduzzo, D; Orlandini, E; Cates, M E; Yeomans, J M

2007-09-01

We report hybrid lattice Boltzmann (HLB) simulations of the hydrodynamics of an active nematic liquid crystal sandwiched between confining walls with various anchoring conditions. We confirm the existence of a transition between a passive phase and an active phase, in which there is spontaneous flow in the steady state. This transition is attained for sufficiently "extensile" rods, in the case of flow-aligning liquid crystals, and for sufficiently "contractile" ones for flow-tumbling materials. In a quasi-one-dimensional geometry, deep in the active phase of flow-aligning materials, our simulations give evidence of hysteresis and history-dependent steady states, as well as of spontaneous banded flow. Flow-tumbling materials, in contrast, rearrange themselves so that only the two boundary layers flow in steady state. Two-dimensional simulations, with periodic boundary conditions, show additional instabilities, with the spontaneous flow appearing as patterns made up of "convection rolls." These results demonstrate a remarkable richness (including dependence on anchoring conditions) in the steady-state phase behavior of active materials, even in the absence of external forcing; they have no counterpart for passive nematics. Our HLB methodology, which combines lattice Boltzmann for momentum transport with a finite difference scheme for the order parameter dynamics, offers a robust and efficient method for probing the complex hydrodynamic behavior of active nematics.

Real-time network security situation visualization and threat assessment based on semi-Markov process

NASA Astrophysics Data System (ADS)

Chen, Junhua

2013-03-01

To cope with a large amount of data in current sensed environments, decision aid tools should provide their understanding of situations in a time-efficient manner, so there is an increasing need for real-time network security situation awareness and threat assessment. In this study, the state transition model of vulnerability in the network based on semi-Markov process is proposed at first. Once events are triggered by an attacker's action or system response, the current states of the vulnerabilities are known. Then we calculate the transition probabilities of the vulnerability from the current state to security failure state. Furthermore in order to improve accuracy of our algorithms, we adjust the probabilities that they exploit the vulnerability according to the attacker's skill level. In the light of the preconditions and post-conditions of vulnerabilities in the network, attack graph is built to visualize security situation in real time. Subsequently, we predict attack path, recognize attack intention and estimate the impact through analysis of attack graph. These help administrators to insight into intrusion steps, determine security state and assess threat. Finally testing in a network shows that this method is reasonable and feasible, and can undertake tremendous analysis task to facilitate administrators' work.

Efficient production of long-lived ultracold Sr2 molecules

NASA Astrophysics Data System (ADS)

Ciamei, Alessio; Bayerle, Alex; Chen, Chun-Chia; Pasquiou, Benjamin; Schreck, Florian

2017-07-01

We associate Sr atom pairs on sites of a Mott insulator optically and coherently into weakly bound ground-state molecules, achieving an efficiency above 80%. This efficiency is 2.5 times higher than in our previous work [S. Stellmer, B. Pasquiou, R. Grimm, and F. Schreck, Phys. Rev. Lett. 109, 115302 (2012), 10.1103/PhysRevLett.109.115302] and obtained through two improvements. First, the lifetime of the molecules is increased beyond one minute by using an optical lattice wavelength that is further detuned from molecular transitions. Second, we compensate undesired dynamic light shifts that occur during the stimulated Raman adiabatic passage (STIRAP) used for molecule association. We also characterize and model STIRAP, providing insights into its limitations. Our work shows that significant molecule association efficiencies can be achieved even for atomic species or mixtures that lack Feshbach resonances suitable for magnetoassociation.

A Gossip-Based Optimistic Replication for Efficient Delay-Sensitive Streaming Using an Interactive Middleware Support System

NASA Astrophysics Data System (ADS)

Mavromoustakis, Constandinos X.; Karatza, Helen D.

2010-06-01

While sharing resources the efficiency is substantially degraded as a result of the scarceness of availability of the requested resources in a multiclient support manner. These resources are often aggravated by many factors like the temporal constraints for availability or node flooding by the requested replicated file chunks. Thus replicated file chunks should be efficiently disseminated in order to enable resource availability on-demand by the mobile users. This work considers a cross layered middleware support system for efficient delay-sensitive streaming by using each device's connectivity and social interactions in a cross layered manner. The collaborative streaming is achieved through the epidemically replicated file chunk policy which uses a transition-based approach of a chained model of an infectious disease with susceptible, infected, recovered and death states. The Gossip-based stateful model enforces the mobile nodes whether to host a file chunk or not or, when no longer a chunk is needed, to purge it. The proposed model is thoroughly evaluated through experimental simulation taking measures for the effective throughput Eff as a function of the packet loss parameter in contrast with the effectiveness of the replication Gossip-based policy.

POSS-Based Electrolyte for Efficient Solid-State Dye-Sensitized Solar Cells at Sub-Zero Temperatures.

PubMed

Lv, Kai; Zhang, Wei; Zhang, Lu; Wang, Zhong-Sheng

2016-03-02

To expand the application of solid-state dye-sensitized solar cells (ssDSSCs) to low temperatures, it is necessary to develop new solid electrolytes with low glass transition temperature (Tg). The Tg is regulated by varying the length of alkyl chain that is connected with the nitrogen atom in the imidazolium ring linked to the polyhedral oligomeric silsesquioxane (POSS). The Tg as low as -8.8 °C is achieved with the POSS grafted with methyl-substituted imidazolium. The effect of alkyl group on the conductivity, Tg, and photovoltaic performance has also been investigated. The conductivity and power conversion efficiency increase with the alkyl length, while the Tg first increases and then decreases with the alkyl length. Among the synthesized POSS-based ionic conductors, the POSS grafted with the methyl-substituted imidazolium yields the highest power conversion efficiency of 6.98% at RT due to its highest conductivity, and the efficiency (6.52%) is still good at -4 °C, as its Tg (-8.8 °C) is lower than the working temperature (-4 °C). This finding suggests that the POSS-based solid electrolyte is promising for subzero-temperature applications of ssDSSCs.

F-state quenching with CH{sub 4} for buffer-gas cooled {sup 171}Y b{sup +} frequency standard

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

Jau, Y.-Y., E-mail: yjau@sandia.gov; Hunker, J. D.; Schwindt, P. D. D.

2015-11-15

We report that methane, CH{sub 4}, can be used as an efficient F-state quenching gas for trapped ytterbium ions. The quenching rate coefficient is measured to be (2.8 ± 0.3) × 10{sup 6} s{sup −1} Torr{sup −1}. For applications that use microwave hyperfine transitions of the ground-state {sup 171}Y b ions, the CH{sub 4} induced frequency shift coefficient and the decoherence rate coefficient are measured as δν/ν = (−3.6 ± 0.1) × 10{sup −6} Torr{sup −1} and 1/T{sub 2} = (1.5 ± 0.2) × 10{sup 5} s{sup −1} Torr{sup −1}. In our buffer-gas cooled {sup 171}Y b{sup +} microwave clockmore » system, we find that only ≤10{sup −8} Torr of CH{sub 4} is required under normal operating conditions to efficiently clear the F-state and maintain ≥85% of trapped ions in the ground state with insignificant pressure shift and collisional decoherence of the clock resonance.« less

Red-luminescence band: A tool for the quality assessment of germanium and silicon nanocrystals

NASA Astrophysics Data System (ADS)

Fraj, I.; Favre, L.; David, T.; Abbarchi, M.; Liu, K.; Claude, J. B.; Ronda, A.; Naffouti, M.; Saidi, F.; Hassen, F.; Maaref, H.; Aqua, J. N.; Berbezier, I.

2017-10-01

We present the photoluminescence (PL) emission of Silicon and Germanium nanocrystals (NCs) of different sizes embedded in two different matrices. Formation of the NCs is achieved via solid-state dewetting during annealing in a molecular beam epitaxy ultra-high vacuum system of ultrathin amorphous Si and Ge layers deposited at room temperature on SiO2. During the dewetting process, the bi-dimensional amorphous layers transform into small pseudo-spherical islands whose mean size can be tuned directly with the deposited thickness. The nanocrystals are capped either ex situ by silicon dioxide or in situ by amorphous Silicon. The surface-state dependent emission (typically in the range 1.74 eV-1.79 eV) exhibited higher relative PL quantum yields compared to the emission originating from the band gap transition. This red-PL emission comes from the radiative transitions between a Si band and an interface level. It is mainly ascribed to the NCs and environment features deduced from morphological and structural analyses. Power dependent analysis of the photoluminescence intensity under continuous excitation reveals a conventional power law with an exponent close to 1, in agreement with the type II nature of the emission. We show that Ge-NCs exhibit much lower quantum efficiency than Si-NCs due to non-radiative interface states. Low quantum efficiency is also obtained when NCs have been exposed to air before capping, even if the exposure time is very short. Our results indicate that a reduction of the non-radiative surface states is a key strategy step in producing small NCs with increased PL emission for a variety of applications. The red-PL band is then an effective tool for the quality assessment of NCs based structures.

Rational design of an enzyme mutant for anti-cocaine therapeutics

NASA Astrophysics Data System (ADS)

Zheng, Fang; Zhan, Chang-Guo

2008-09-01

(-)-Cocaine is a widely abused drug and there is no available anti-cocaine therapeutic. The disastrous medical and social consequences of cocaine addiction have made the development of an effective pharmacological treatment a high priority. An ideal anti-cocaine medication would be to accelerate (-)-cocaine metabolism producing biologically inactive metabolites. The main metabolic pathway of cocaine in body is the hydrolysis at its benzoyl ester group. Reviewed in this article is the state-of-the-art computational design of high-activity mutants of human butyrylcholinesterase (BChE) against (-)-cocaine. The computational design of BChE mutants have been based on not only the structure of the enzyme, but also the detailed catalytic mechanisms for BChE-catalyzed hydrolysis of (-)-cocaine and (+)-cocaine. Computational studies of the detailed catalytic mechanisms and the structure-and-mechanism-based computational design have been carried out through the combined use of a variety of state-of-the-art techniques of molecular modeling. By using the computational insights into the catalytic mechanisms, a recently developed unique computational design strategy based on the simulation of the rate-determining transition state has been employed to design high-activity mutants of human BChE for hydrolysis of (-)-cocaine, leading to the exciting discovery of BChE mutants with a considerably improved catalytic efficiency against (-)-cocaine. One of the discovered BChE mutants (i.e., A199S/S287G/A328W/Y332G) has a ˜456-fold improved catalytic efficiency against (-)-cocaine. The encouraging outcome of the computational design and discovery effort demonstrates that the unique computational design approach based on the transition-state simulation is promising for rational enzyme redesign and drug discovery.

Understanding the Intrinsic Electrochemistry of Ni-Rich Layered Cathodes

NASA Astrophysics Data System (ADS)

Sallis, Shawn

The demand for energy is continually increasing overtime and the key to meeting future demand in a sustainable way is with energy storage. Li-ion batteries employing layered transition metal oxide cathodes are one of the most technologically important energy storage technologies. However, current Li-ion batteries are unable to access their full theoretical capacity and suffer from performance limiting degradation over time partially originating from the cathode and partially from the interface with the electrolyte. Understanding the fundamental limitations of layered transition metal oxide cathodes requires a complete understanding of the surface and bulk of the materials in their most delithiated state. In this thesis, we employ LiNi0.8Co0.15Al 0.05O2 (NCA) as a model system for Ni-rich layered oxide cathodes. Unlike its parent compound, LiCoO2, NCA is capable of high states of delithiation with minimal structural transitions. Furthermore, commercially available NCA has little to no transition metals in the Li layer. X-ray spectroscopies are an ideal tool for studying cathodes at high states of delithiation due their elemental selectivity, range of probing depths, and sensitivity to both chemical and electronic state information. The oxidation state of the transition metals at the surface can be probed via X-ray photoelectron spectroscopy (XPS) while both bulk and surface oxidation states as well as changes in metal oxygen bonding can be probed using X-ray absorption spectroscopy (XAS). Using X-ray spectroscopy in tandem with electrochemical, transport and microscopy measurements of the same materials, the impedance growth with increasing delithiation was correlated with the formation of a disordered NiO phase on the surface of NCA which was precipitated by the release of oxygen. Furthermore, the surface degradation was strongly impacted by the type of Li salt used in the electrolyte, with the standard commercial salt LiPF6 suffering from exothermic decomposition at high voltages and temperatures. Substituting LiPF6with LiBF4 suppressed NCA surface degradation and the dissolution of the transition metals into the electrolyte which is responsible for the impedance growth. Even in the most extreme conditions (4.75V vs Li +/Li0 at 60 °C for > 100 hrs) the degradation (i.e. metal reduction) was restricted to the first 10-30 nm and no evidence of oxygen loss was observed in the bulk. However, the transition metal ions were found to cease oxidizing above 4.25 V vs Li+/Li0 despite it being possible to extract 20% more lithium. Using a newly developed high efficiency resonant inelastic x-ray scattering (RIXS) spectrometer to probe the O K-edge of NCA electrodes at various conditions, it was concluded that oxygen participates in the charge compensation at the highest states of delithiation instead of the transition metals. These results are intrinsic to the physical and electronic structure of NCA and appear general to the other layered transition metal oxides currently under consideration for use as cathodes in Li-ion batteries.

Household energy management strategies in Bulgaria's transitioning energy sector

NASA Astrophysics Data System (ADS)

Carper, Mark Daniel Lynn

Recent transition literature of post-socialist states has addressed the shortcomings of a rapid blanket implementation of neo-liberal policies and practices placed upon a landscape barren of the needed institutions and experiences. Included in these observations are the policy-making oversight of spatial socioeconomic variations and their individual and diverse methods of coping with their individual challenges. Of such literature addressing the case of Bulgaria, a good portion deals with the spatial consequences of restructuring as well as with embedded disputes over access to and control of resources. With few exceptions, studies of Bulgaria's changing energy sector have largely been at the state level and have not been placed within the context of spatial disparities of socioeconomic response. By exploring the variations of household energy management strategies across space, my dissertation places this resource within such a theoretical context and offers analysis based on respective levels of economic and human development, inherited material infrastructures, the organization and activities of institutions, and fuel and technological availability. A closed survey was distributed to explore six investigational themes across four geographic realms. The investigational themes include materials of housing construction, methods of household heating, use of electrical appliances, energy conservation strategies, awareness and use of energy conservation technologies, and attitudes toward the transitioning energy sector. The geographic realms include countrywide results, the urban-rural divide, regional variations, and urban divisions of the capital city, Sofia. Results conclude that, indeed, energy management strategies at the household level have been shaped by multiple variables, many of which differ across space. These variables include price sensitivity, degree of dependence on remnant technologies, fuel and substitute availability, and level of human and socioeconomic development. Thus far, the state has taken a very limited role in improving residential energy efficiency despite the increased energy expenditure burdens that most households face. Yet lacking are affordable technologies, educational campaigns, and individual financing mechanisms or incentives. As shown, where there is an informed, active, and financially capable population, improved household efficiency is more likely to be the winning strategy for both the goals of the individual as well as of the state.

Algorithms for Performance, Dependability, and Performability Evaluation using Stochastic Activity Networks

NASA Technical Reports Server (NTRS)

Deavours, Daniel D.; Qureshi, M. Akber; Sanders, William H.

1997-01-01

Modeling tools and technologies are important for aerospace development. At the University of Illinois, we have worked on advancing the state of the art in modeling by Markov reward models in two important areas: reducing the memory necessary to numerically solve systems represented as stochastic activity networks and other stochastic Petri net extensions while still obtaining solutions in a reasonable amount of time, and finding numerically stable and memory-efficient methods to solve for the reward accumulated during a finite mission time. A long standing problem when modeling with high level formalisms such as stochastic activity networks is the so-called state space explosion, where the number of states increases exponentially with size of the high level model. Thus, the corresponding Markov model becomes prohibitively large and solution is constrained by the the size of primary memory. To reduce the memory necessary to numerically solve complex systems, we propose new methods that can tolerate such large state spaces that do not require any special structure in the model (as many other techniques do). First, we develop methods that generate row and columns of the state transition-rate-matrix on-the-fly, eliminating the need to explicitly store the matrix at all. Next, we introduce a new iterative solution method, called modified adaptive Gauss-Seidel, that exhibits locality in its use of data from the state transition-rate-matrix, permitting us to cache portions of the matrix and hence reduce the solution time. Finally, we develop a new memory and computationally efficient technique for Gauss-Seidel based solvers that avoids the need for generating rows of A in order to solve Ax = b. This is a significant performance improvement for on-the-fly methods as well as other recent solution techniques based on Kronecker operators. Taken together, these new results show that one can solve very large models without any special structure.

Modeling and simulation of radiation from hypersonic flows with Monte Carlo methods

NASA Astrophysics Data System (ADS)

Sohn, Ilyoup

During extreme-Mach number reentry into Earth's atmosphere, spacecraft experience hypersonic non-equilibrium flow conditions that dissociate molecules and ionize atoms. Such situations occur behind a shock wave leading to high temperatures, which have an adverse effect on the thermal protection system and radar communications. Since the electronic energy levels of gaseous species are strongly excited for high Mach number conditions, the radiative contribution to the total heat load can be significant. In addition, radiative heat source within the shock layer may affect the internal energy distribution of dissociated and weakly ionized gas species and the number density of ablative species released from the surface of vehicles. Due to the radiation total heat load to the heat shield surface of the vehicle may be altered beyond mission tolerances. Therefore, in the design process of spacecrafts the effect of radiation must be considered and radiation analyses coupled with flow solvers have to be implemented to improve the reliability during the vehicle design stage. To perform the first stage for radiation analyses coupled with gas-dynamics, efficient databasing schemes for emission and absorption coefficients were developed to model radiation from hypersonic, non-equilibrium flows. For bound-bound transitions, spectral information including the line-center wavelength and assembled parameters for efficient calculations of emission and absorption coefficients are stored for typical air plasma species. Since the flow is non-equilibrium, a rate equation approach including both collisional and radiatively induced transitions was used to calculate the electronic state populations, assuming quasi-steady-state (QSS). The Voigt line shape function was assumed for modeling the line broadening effect. The accuracy and efficiency of the databasing scheme was examined by comparing results of the databasing scheme with those of NEQAIR for the Stardust flowfield. An accuracy of approximately 1 % was achieved with an efficiency about three times faster than the NEQAIR code. To perform accurate and efficient analyses of chemically reacting flowfield - radiation interactions, the direct simulation Monte Carlo (DSMC) and the photon Monte Carlo (PMC) radiative transport methods are used to simulate flowfield - radiation coupling from transitional to peak heating freestream conditions. The non-catalytic and fully catalytic surface conditions were modeled and good agreement of the stagnation-point convective heating between DSMC and continuum fluid dynamics (CFD) calculation under the assumption of fully catalytic surface was achieved. Stagnation-point radiative heating, however, was found to be very different. To simulate three-dimensional radiative transport, the finite-volume based PMC (FV-PMC) method was employed. DSMC - FV-PMC simulations with the goal of understanding the effect of radiation on the flow structure for different degrees of hypersonic non-equilibrium are presented. It is found that except for the highest altitudes, the coupling of radiation influences the flowfield, leading to a decrease in both heavy particle translational and internal temperatures and a decrease in the convective heat flux to the vehicle body. The DSMC - FV-PMC coupled simulations are compared with the previous coupled simulations and correlations obtained using continuum flow modeling and one-dimensional radiative transport. The modeling of radiative transport is further complicated by radiative transitions occurring during the excitation process of the same radiating gas species. This interaction affects the distribution of electronic state populations and, in turn, the radiative transport. The radiative transition rate in the excitation/de-excitation processes and the radiative transport equation (RTE) must be coupled simultaneously to account for non-local effects. The QSS model is presented to predict the electronic state populations of radiating gas species taking into account non-local radiation. The definition of the escape factor which is dependent on the incoming radiative intensity from over all directions is presented. The effect of the escape factor on the distribution of electronic state populations of the atomic N and O radiating species is examined in a highly non-equilibrium flow condition using DSMC and PMC methods and the corresponding change of the radiative heat flux due to the non-local radiation is also investigated.

Charge reconfiguration in arrays of quantum dots

NASA Astrophysics Data System (ADS)

Bayer, Johannes C.; Wagner, Timo; Rugeramigabo, Eddy P.; Haug, Rolf J.

2017-12-01

Semiconductor quantum dots are potential building blocks for scalable qubit architectures. Efficient control over the exchange interaction and the possibility of coherently manipulating electron states are essential ingredients towards this goal. We studied experimentally the shuttling of electrons trapped in serial quantum dot arrays isolated from the reservoirs. The isolation hereby enables a high degree of control over the tunnel couplings between the quantum dots, while electrons can be transferred through the array by gate voltage variations. Model calculations are compared with our experimental results for double, triple, and quadruple quantum dot arrays. We are able to identify all transitions observed in our experiments, including cotunneling transitions between distant quantum dots. The shuttling of individual electrons between quantum dots along chosen paths is demonstrated.

Constant pH Molecular Dynamics in Explicit Solvent with Enveloping Distribution Sampling and Hamiltonian Exchange

PubMed Central

2015-01-01

We present a new computational approach for constant pH simulations in explicit solvent based on the combination of the enveloping distribution sampling (EDS) and Hamiltonian replica exchange (HREX) methods. Unlike constant pH methods based on variable and continuous charge models, our method is based on discrete protonation states. EDS generates a hybrid Hamiltonian of different protonation states. A smoothness parameter s is used to control the heights of energy barriers of the hybrid-state energy landscape. A small s value facilitates state transitions by lowering energy barriers. Replica exchange between EDS potentials with different s values allows us to readily obtain a thermodynamically accurate ensemble of multiple protonation states with frequent state transitions. The analysis is performed with an ensemble obtained from an EDS Hamiltonian without smoothing, s = ∞, which strictly follows the minimum energy surface of the end states. The accuracy and efficiency of this method is tested on aspartic acid, lysine, and glutamic acid, which have two protonation states, a histidine with three states, a four-residue peptide with four states, and snake cardiotoxin with eight states. The pKa values estimated with the EDS-HREX method agree well with the experimental pKa values. The mean absolute errors of small benchmark systems range from 0.03 to 0.17 pKa units, and those of three titratable groups of snake cardiotoxin range from 0.2 to 1.6 pKa units. This study demonstrates that EDS-HREX is a potent theoretical framework, which gives the correct description of multiple protonation states and good calculated pKa values. PMID:25061443

Blue diode-pumped solid-state-laser based on ytterbium doped laser crystals operating on the resonance zero-phonon transition

DOEpatents

Krupke, William F.; Payne, Stephen A.; Marshall, Christopher D.

2001-01-01

The invention provides an efficient, compact means of generating blue laser light at a wavelength near .about.493+/-3 nm, based on the use of a laser diode-pumped Yb-doped laser crystal emitting on its zero phonon line (ZPL) resonance transition at a wavelength near .about.986+/-6 nm, whose fundamental infrared output radiation is harmonically doubled into the blue spectral region. The invention is applied to the excitation of biofluorescent dyes (in the .about.490-496 nm spectral region) utilized in flow cytometry, immunoassay, DNA sequencing, and other biofluorescence instruments. The preferred host crystals have strong ZPL fluorecence (laser) transitions lying in the spectral range from .about.980 to .about.992 nm (so that when frequency-doubled, they produce output radiation in the spectral range from 490 to 496 nm). Alternate preferred Yb doped tungstate crystals, such as Yb:KY(WO.sub.4).sub.2, may be configured to lase on the resonant ZPL transition near 981 nm (in lieu of the normal 1025 nm transition). The laser light is then doubled in the blue at 490.5 nm.

Assessing the implementation of a bedside service handoff on an academic hospitalist service.

PubMed

Wray, Charlie M; Arora, Vineet M; Hedeker, Donald; Meltzer, David O

2018-06-01

Inpatient service handoffs are a vulnerable transition during a patients' hospitalization. We hypothesized that performing the service handoff at the patients' bedside may be one mechanism to more efficiently transfer patient information between physicians, while further integrating the patient into their hospital care. We performed a 6-month prospective study of performing a bedside handoff (BHO) at the service transition on a non-teaching hospitalist service. On a weekly basis, transitioning hospitalists co-rounded at patient's bedsides. Post-handoff surveys assessed for completeness of handoff, communication, missed information, and adverse events. A control group who performed the handoff via email, phone or face-to-face was also surveyed. Chi-square and item-response theory (IRT) analysis assessed for differences between BHO and control groups. Narrative responses were elicited to qualitatively describe the BHO. In total, 21/31 (67%) scheduled BHOs were performed. On average, 4 out of 6 eligible patients experienced a BHO, with a total of 90 patients experiencing a BHO. Of those asked to perform the BHO, 52% stated the service transition took 31-60 min compared to 24% in the control group. Controlling for the nesting of observations within physicians, IRT analysis found that BHO respondents had statistically significant greater odds of: reporting increased patient awareness of the service handoff, more certainty in the plan for each patient, less discovery of missed information, and less time needed to learn about the patient on the first day compared to control methods. Narrative responses described a more patient-centered handoff with improved communication that was time-consuming and often logistically difficult to implement. Despite its time-intensive nature, performing the service handoff at the patient's bedside may lead to a more complete and efficient service transition. Published by Elsevier Inc.

Quantum Vertex Model for Reversible Classical Computing

NASA Astrophysics Data System (ADS)

Chamon, Claudio; Mucciolo, Eduardo; Ruckenstein, Andrei; Yang, Zhicheng

We present a planar vertex model that encodes the result of a universal reversible classical computation in its ground state. The approach involves Boolean variables (spins) placed on links of a two-dimensional lattice, with vertices representing logic gates. Large short-ranged interactions between at most two spins implement the operation of each gate. The lattice is anisotropic with one direction corresponding to computational time, and with transverse boundaries storing the computation's input and output. The model displays no finite temperature phase transitions, including no glass transitions, independent of circuit. The computational complexity is encoded in the scaling of the relaxation rate into the ground state with the system size. We use thermal annealing and a novel and more efficient heuristic \\x9Dannealing with learning to study various computational problems. To explore faster relaxation routes, we construct an explicit mapping of the vertex model into the Chimera architecture of the D-Wave machine, initiating a novel approach to reversible classical computation based on quantum annealing.

SELF-SUSTAINED RECYCLING IN THE INNER DUST RING OF PRE-TRANSITIONAL DISKS

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

Husmann, T.; Loesche, C.; Wurm, G., E-mail: tim.jankowski@uni-due.de

Observations of pre-transitional disks show a narrow inner dust ring and a larger outer one. They are separated by a cavity with no or only little dust. We propose an efficient recycling mechanism for the inner dust ring which keeps it in a steady state. No major particle sources are needed for replenishment. Dust particles and pebbles drift outwards by radiation pressure and photophoresis. The pebbles grow during outward drift until they reach a balanced position where residual gravity compensates photophoresis. While still growing larger they reverse their motion and drift inward. Eventually, their speed is fast enough for themmore » to be destroyed in collisions with other pebbles and drift outward again. We quantify the force balance and drift velocities for the disks LkCa15 and HD 135344B. We simulate single-particle evolution and show that this scenario is viable. Growth and drift timescales are on the same order and a steady state can be established in the inner dust ring.« less

An investigation of one- versus two-dimensional semiclassical transition state theory for H atom abstraction and exchange reactions.

PubMed

Greene, Samuel M; Shan, Xiao; Clary, David C

2016-02-28

We investigate which terms in Reduced-Dimensionality Semiclassical Transition State Theory (RD SCTST) contribute most significantly in rate constant calculations of hydrogen extraction and exchange reactions of hydrocarbons. We also investigate the importance of deep tunneling corrections to the theory. In addition, we introduce a novel formulation of the theory in Jacobi coordinates. For the reactions of H atoms with methane, ethane, and cyclopropane, we find that a one-dimensional (1-D) version of the theory without deep tunneling corrections compares well with 2-D SCTST results and accurate quantum scattering results. For the "heavy-light-heavy" H atom exchange reaction between CH3 and CH4, deep tunneling corrections are needed to yield 1-D results that compare well with 2-D results. The finding that accurate rate constants can be obtained from derivatives of the potential along only one dimension further validates RD SCTST as a computationally efficient yet accurate rate constant theory.

n l -> n' l' transition rates in electron and proton - Rydberg atom collision

NASA Astrophysics Data System (ADS)

Vrinceanu, Daniel

2017-04-01

Electrons and protons drive the recombination dynamics of highly excited Rydberg atoms in cold rarefied plasmas found in astrophysical conditions such as primordial recombination or star formation in H-II clouds. It has been recognized that collisions induce both energy and angular momentum transitions in Rydberg atoms, although in different proportions, depending on the initial state, temperature and the given species considered in the collision (electron or proton). Most studies focused on one collision type at a time, under the assumption that collision types are independent or their effects are not competing. The classical Monte-Carlo trajectory simulations presented in this work calculate the rates for both energy and angular momentum transfers and show their interdependence. For example, energy transfer with small angular momentum change are more efficient for target states with initial large angular momentum. The author acknowledges support received from the National Science Foundation through a Grant for the Center for Research on Complex Networks (HRD-1137732).

An automated method to find transition states using chemical dynamics simulations.

PubMed

Martínez-Núñez, Emilio

2015-02-05

A procedure to automatically find the transition states (TSs) of a molecular system (MS) is proposed. It has two components: high-energy chemical dynamics simulations (CDS), and an algorithm that analyzes the geometries along the trajectories to find reactive pathways. Two levels of electronic structure calculations are involved: a low level (LL) is used to integrate the trajectories and also to optimize the TSs, and a higher level (HL) is used to reoptimize the structures. The method has been tested in three MSs: formaldehyde, formic acid (FA), and vinyl cyanide (VC), using MOPAC2012 and Gaussian09 to run the LL and HL calculations, respectively. Both the efficacy and efficiency of the method are very good, with around 15 TS structures optimized every 10 trajectories, which gives a total of 7, 12, and 83 TSs for formaldehyde, FA, and VC, respectively. The use of CDS makes it a powerful tool to unveil possible nonstatistical behavior of the system under study. © 2014 Wiley Periodicals, Inc.

Movement-related and steady-state electromyographic activity of human elbow flexors in slow transition movements between two equilibrium states.

PubMed

Tal'nov, A N; Cherkassky, V L; Kostyukov, A I

1997-08-01

The electromyograms were recorded in healthy human subjects by surface electrodes from the mm. biceps brachii (caput longum et. brevis), brachioradialis, and triceps brachii (caput longum) during slow transition movements in elbow joint against a weak extending torque. The test movements (flexion transitions between two steady-states) were fulfilled under visual control through combining on a monitor screen a signal from a joint angle sensor with a corresponding command generated by a computer. Movement velocities ranged between 5 and 80 degrees/s, subjects were asked to move forearm without activation of elbow extensors. Surface electromyograms were full-wave rectified, filtered and averaged within sets of 10 identical tests. Amplitudes of dynamic and steady-state components of the electromyograms were determined in dependence on a final value of joint angle, slow and fast movements were compared. An exponential-like increase of dynamic component was observed in electromyograms recorded from m. biceps brachii, the component had been increased with movement velocity and with load increment. In many experiments a statistically significant decrease of static component could be noticed within middle range of joint angles (40-60 degrees) followed by a well expressed increment for larger movements. This pattern of the static component in electromyograms could vary in different experiments even in the same subjects. A steady discharge in m. brachioradialis at ramp phase has usually been recorded only under a notable load. Variable and quite often unpredictable character of the static components of the electromyograms recorded from elbow flexors in the transition movements makes it difficult to use the equilibrium point hypothesis to describe the central processes of movement. It has been assumed that during active muscle shortening the dynamic components in arriving efferent activity should play a predominant role. A simple scheme could be proposed for transition to a steady-state after shortening. Decrease of the efferent inflow can evoke internal lengthening of the contractile elements in muscle and, as a result, hysteresis increase in the muscle contraction efficiency. Effectiveness in maintenance of the steady position seems to also be enhanced due to muscle thixotropy and friction processes in the joint. Hysteresis after-effects in elbow flexors were demonstrated as a difference in steady-state levels of electromyograms with oppositely directed approaches to the same joint position.

Semiempirical modeling of Ag nanoclusters: New parameters for optical property studies enable determination of double excitation contributions to plasmonic excitation

DOE PAGES

Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C.

2016-06-03

Quantum mechanical studies of Ag nanoclusters have shown that plasmonic behavior can be modeled in terms of excited states where collectivity among single excitations leads to strong absorption. However, new computational approaches are needed to provide understanding of plasmonic excitations beyond the single-excitation level. We show that semiempirical INDO/CI approaches with appropriately selected parameters reproduce the TD-DFT optical spectra of various closed-shell Ag clusters. The plasmon-like states with strong optical absorption comprise linear combinations of many singly excited configurations that contribute additively to the transition dipole moment, whereas all other excited states show significant cancellation among the contributions to themore » transition dipole moment. The computational efficiency of this approach allows us to investigate the role of double excitations at the INDO/SDCI level. The Ag cluster ground states are stabilized by slight mixing with doubly excited configurations, but the plasmonic states generally retain largely singly excited character. The consideration of double excitations in all cases improves the agreement of the INDO/CI absorption spectra with TD-DFT, suggesting that the SDCI calculation effectively captures some of the ground-state correlation implicit in DFT. Furthermore, these results provide the first evidence to support the commonly used assumption that single excitations are in many cases sufficient to describe the optical spectra of plasmonic excitations quantum mechanically.« less

Time-dependent evolution of cosmic-ray-modified shock structure: Transition to steady state

NASA Astrophysics Data System (ADS)

Donohue, D. J.; Zank, G. P.; Webb, G. M.

1994-03-01

Steady state solutions to the two-fluid equations of cosmic-ray-modified shock structure were investigated first by Drury and Volk (1981). Their analysis revealed, among other properties, that there exist regions of upstream parameter space where the equations possess three different downstream solutions for a given upstream state. In this paper we investigate whether or not all these solutions can occur as time-asymptotic states in a physically realistic evolution. To do this, we investigate the time-dependent evolution of the two-fluid cosmic-ray equations in going from a specified initial condition to a steady state. Our results indicate that the time-asymptotic solution is strictly single-valued, and it undergoes a transition from weakly to strongly cosmic-ray-modified at a critical value of the upstream cosmic ray energy density. The expansion of supernova remnant shocks is considered as an example, and it is shown that the strong to weak transition is in fact more likely. The third intermediate solution is shown to influence the time-dependent evolution of the shock, but it is not found to be a stable time-asymptotic state. Timescales for convergence to these states and their implications for the efficiency of shock acceleration are considered. We also investigate the effects of a recently introduced model for the injection of seed particles into the shock accelerated cosmic-ray population. The injection is found to result in a more strongly cosmic-ray-dominated shock, which supports our conclusion that for most classes of intermediate and strong cosmic-ray-modified shocks, the downstream cosmic-ray pressure component is at least as large as the thermal gas pressure, independent of the upstream state. As a result, cosmic rays almost always play a significant role in determining the shock structure and dissipation and they cannot be regarded as test particles.

Time-dependent evolution of cosmic-ray-modified shock structure: Transition to steady state

NASA Technical Reports Server (NTRS)

Donohue, D. J.; Zank, G. P.; Webb, G. M.

1994-01-01

Steady state solutions to the two-fluid equations of cosmic-ray-modified shock structure were investigated first by Drury and Volk (1981). Their analysis revealed, among other properties, that there exist regions of upstream parameter space where the equations possess three different downstream solutions for a given upstream state. In this paper we investigate whether or not all these solutions can occur as time-asymptotic states in a physically realistic evolution. To do this, we investigate the time-dependent evolution of the two-fluid cosmic-ray equations in going from a specified initial condition to a steady state. Our results indicate that the time-asymptotic solution is strictly single-valued, and it undergoes a transition from weakly to strongly cosmic-ray-modified at a critical value of the upstream cosmic ray energy density. The expansion of supernova remnant shocks is considered as an example, and it is shown that the strong to weak transition is in fact more likely. The third intermediate solution is shown to influence the time-dependent evolution of the shock, but it is not found to be a stable time-asymptotic state. Timescales for convergence to these states and their implications for the efficiency of shock acceleration are considered. We also investigate the effects of a recently introduced model for the injection of seed particles into the shock accelerated cosmic-ray population. The injection is found to result in a more strongly cosmic-ray-dominated shock, which supports our conclusion that for most classes of intermediate and strong cosmic-ray-modified shocks, the downstream cosmic-ray pressure component is at least as large as the thermal gas pressure, independent of the upstream state. As a result, cosmic rays almost always play a significant role in determining the shock structure and dissipation and they cannot be regarded as test particles.

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.

Efficient transportation for Vermont : optimal statewide transit networks.

DOT National Transportation Integrated Search

2011-01-01

"Public transit systems are receiving increased attention as viable solutions to problems with : transportation system robustness, energy-efficiency and equity. The over-reliance on a single : mode, the automobile, is a threat to system robustness. I...

A new window towards multidimensional sensing of transition metal cations through dual mode sensing ability of N-benzyl-(3-hydoxy-2-naphthalene): Emission enhancement coupled remarkable spectral shift

NASA Astrophysics Data System (ADS)

Paul, Bijan Kumar; Mahanta, Subrata; Singh, Rupashree Balia; Guchhait, Nikhil

2011-06-01

A structurally simple Schiff base N-benzyl-(3-hydroxy-2-naphthalene) (NBHN32) has been synthesized and characterized by 1H NMR, 13C NMR, and DEPT spectroscopy. The photophysical behaviour of NBHN32 in response to the presence of various transition metal cations has been explored by means of steady-state absorption, emission and time-resolved emission spectroscopy techniques. Efficient through space intramolecular photoinduced electron transfer (PET) between the naphthalene fluorophore and the imine group has been argued for extremely low fluorescence yield of NBHN32 compared to the parent molecule 3-hydroxy-2-naphthaldehyde (HN32) containing the same fluorophore but lacking the receptor moiety. Transition metal ion-induced emission enhancement is thus addressed on the lexicon of perturbation of the PET by the metal ions. Apart from fluorescence enhancement, transition metal ion imparts remarkable shift of the emission maxima of NBHN32, which is another unique aspect on the proposed ability of NBHN32 to function as a fluorescence chemosensor.

Machine learning vortices at the Kosterlitz-Thouless transition

NASA Astrophysics Data System (ADS)

Beach, Matthew J. S.; Golubeva, Anna; Melko, Roger G.

2018-01-01

Efficient and automated classification of phases from minimally processed data is one goal of machine learning in condensed-matter and statistical physics. Supervised algorithms trained on raw samples of microstates can successfully detect conventional phase transitions via learning a bulk feature such as an order parameter. In this paper, we investigate whether neural networks can learn to classify phases based on topological defects. We address this question on the two-dimensional classical XY model which exhibits a Kosterlitz-Thouless transition. We find significant feature engineering of the raw spin states is required to convincingly claim that features of the vortex configurations are responsible for learning the transition temperature. We further show a single-layer network does not correctly classify the phases of the XY model, while a convolutional network easily performs classification by learning the global magnetization. Finally, we design a deep network capable of learning vortices without feature engineering. We demonstrate the detection of vortices does not necessarily result in the best classification accuracy, especially for lattices of less than approximately 1000 spins. For larger systems, it remains a difficult task to learn vortices.

Cell transmission model of dynamic assignment for urban rail transit networks.

PubMed

Xu, Guangming; Zhao, Shuo; Shi, Feng; Zhang, Feilian

2017-01-01

For urban rail transit network, the space-time flow distribution can play an important role in evaluating and optimizing the space-time resource allocation. For obtaining the space-time flow distribution without the restriction of schedules, a dynamic assignment problem is proposed based on the concept of continuous transmission. To solve the dynamic assignment problem, the cell transmission model is built for urban rail transit networks. The priority principle, queuing process, capacity constraints and congestion effects are considered in the cell transmission mechanism. Then an efficient method is designed to solve the shortest path for an urban rail network, which decreases the computing cost for solving the cell transmission model. The instantaneous dynamic user optimal state can be reached with the method of successive average. Many evaluation indexes of passenger flow can be generated, to provide effective support for the optimization of train schedules and the capacity evaluation for urban rail transit network. Finally, the model and its potential application are demonstrated via two numerical experiments using a small-scale network and the Beijing Metro network.

Spectrally-Temporally Adapted Spectrally Modulated Spectrally Encoded (SMSE) Waveform Design for Coexistent CR-Based SDR Applications

DTIC Science & Technology

2010-03-01

uses all available resources in some optimized manner. By further exploiting the design flexibility and computational efficiency of Orthogonal Frequency...in the following sections. 3.2.1 Estimation of PU Signal Statistics. The Estimate PU Signal Statis- tics function of Fig 3.4 is used to compute the...consecutive PU transmissions, and 4) the probability of transitioning from one transmission state to another. These statistics are then used to compute the

State Transition Matrix for Perturbed Orbital Motion Using Modified Chebyshev Picard Iteration

NASA Astrophysics Data System (ADS)

Read, Julie L.; Younes, Ahmad Bani; Macomber, Brent; Turner, James; Junkins, John L.

2015-06-01

The Modified Chebyshev Picard Iteration (MCPI) method has recently proven to be highly efficient for a given accuracy compared to several commonly adopted numerical integration methods, as a means to solve for perturbed orbital motion. This method utilizes Picard iteration, which generates a sequence of path approximations, and Chebyshev Polynomials, which are orthogonal and also enable both efficient and accurate function approximation. The nodes consistent with discrete Chebyshev orthogonality are generated using cosine sampling; this strategy also reduces the Runge effect and as a consequence of orthogonality, there is no matrix inversion required to find the basis function coefficients. The MCPI algorithms considered herein are parallel-structured so that they are immediately well-suited for massively parallel implementation with additional speedup. MCPI has a wide range of applications beyond ephemeris propagation, including the propagation of the State Transition Matrix (STM) for perturbed two-body motion. A solution is achieved for a spherical harmonic series representation of earth gravity (EGM2008), although the methodology is suitable for application to any gravity model. Included in this representation the normalized, Associated Legendre Functions are given and verified numerically. Modifications of the classical algorithm techniques, such as rewriting the STM equations in a second-order cascade formulation, gives rise to additional speedup. Timing results for the baseline formulation and this second-order formulation are given.

Coherent Microwave-to-Optical Conversion via Six-Wave Mixing in Rydberg Atoms

NASA Astrophysics Data System (ADS)

Han, Jingshan; Vogt, Thibault; Gross, Christian; Jaksch, Dieter; Kiffner, Martin; Li, Wenhui

2018-03-01

We present an experimental demonstration of converting a microwave field to an optical field via frequency mixing in a cloud of cold 87Rb atoms, where the microwave field strongly couples to an electric dipole transition between Rydberg states. We show that the conversion allows the phase information of the microwave field to be coherently transferred to the optical field. With the current energy level scheme and experimental geometry, we achieve a photon-conversion efficiency of ˜0.3 % at low microwave intensities and a broad conversion bandwidth of more than 4 MHz. Theoretical simulations agree well with the experimental data, and they indicate that near-unit efficiency is possible in future experiments.

HRSSA - Efficient hybrid stochastic simulation for spatially homogeneous biochemical reaction networks

NASA Astrophysics Data System (ADS)

Marchetti, Luca; Priami, Corrado; Thanh, Vo Hong

2016-07-01

This paper introduces HRSSA (Hybrid Rejection-based Stochastic Simulation Algorithm), a new efficient hybrid stochastic simulation algorithm for spatially homogeneous biochemical reaction networks. HRSSA is built on top of RSSA, an exact stochastic simulation algorithm which relies on propensity bounds to select next reaction firings and to reduce the average number of reaction propensity updates needed during the simulation. HRSSA exploits the computational advantage of propensity bounds to manage time-varying transition propensities and to apply dynamic partitioning of reactions, which constitute the two most significant bottlenecks of hybrid simulation. A comprehensive set of simulation benchmarks is provided for evaluating performance and accuracy of HRSSA against other state of the art algorithms.

Fast optical cooling of a nanomechanical cantilever by a dynamical Stark-shift gate.

PubMed

Yan, Leilei; Zhang, Jian-Qi; Zhang, Shuo; Feng, Mang

2015-10-12

The efficient cooling of nanomechanical resonators is essential to exploration of quantum properties of the macroscopic or mesoscopic systems. We propose such a laser-cooling scheme for a nanomechanical cantilever, which works even for the low-frequency mechanical mode and under weak cooling lasers. The cantilever is coupled by a diamond nitrogen-vacancy center under a strong magnetic field gradient and the cooling is assisted by a dynamical Stark-shift gate. Our scheme can effectively enhance the desired cooling efficiency by avoiding the off-resonant and undesired carrier transitions, and thereby cool the cantilever down to the vicinity of the vibrational ground state in a fast fashion.

Fast optical cooling of a nanomechanical cantilever by a dynamical Stark-shift gate

PubMed Central

Yan, Leilei; Zhang, Jian-Qi; Zhang, Shuo; Feng, Mang

2015-01-01

The efficient cooling of nanomechanical resonators is essential to exploration of quantum properties of the macroscopic or mesoscopic systems. We propose such a laser-cooling scheme for a nanomechanical cantilever, which works even for the low-frequency mechanical mode and under weak cooling lasers. The cantilever is coupled by a diamond nitrogen-vacancy center under a strong magnetic field gradient and the cooling is assisted by a dynamical Stark-shift gate. Our scheme can effectively enhance the desired cooling efficiency by avoiding the off-resonant and undesired carrier transitions, and thereby cool the cantilever down to the vicinity of the vibrational ground state in a fast fashion. PMID:26455901

Comparative research on medicine application with 0.53-um, 1.06-um, and 1.32-um Nd:YAG lasers

NASA Astrophysics Data System (ADS)

Li, Yahua; Li, Zhenjia; Zhu, Changhong; Huang, Yizhong

1996-09-01

Because of its high power and excellent optical features, laser has almost been applied to everywhere of medical research and clinic. Over the past several years, laser medical has achieved a rapid progress, and laser medical instruments has developed promptly, each new wavelength can be successfully applied in diagnostic and treatment of diseases. Among the medical lasers, Nd:YAG solid-state laser systems have proven useful in surgical use operate, such as neurosurgery, gastroenterology, cardioangiology, urology, gynecology, dermatology and ENT. As with other solid-state lasers, the Nd:YAG laser can be made to emit various wavelengths by means of suitable resonator configurations and some newest solid-state laser technology, pumped by the Krypton lamp, the Nd:YAG laser at room temperature exhibits transition at 1.06 micrometer Nd:YAG, using nonlinear crystal and Q-switch to double its frequency can attain 0.53 micrometer green beam. In our laser systems, the efficiency at 1.06 micrometer is more than 3 percent, an efficiency of 0.5 percent at 1.32 micrometer and 0.53 micrometer can be attained. For a power of 100w at 1.06 micrometer, 15w at 1.32 micrometer and 0.53 micrometer can therefore be produced. All of three kinds Nd:YAG laser hold these characteristics: high output power; optical fiber transition that can be cooperated with endoscope. The paper mainly discusses laser operating characteristics and clinic applications of three kinds wavelengths at 0.53 micrometer 1.06 micrometer and 1.32 micrometer Nd:YAG laser systems.

Generalized Buneman Pruning for Inferring the Most Parsimonious Multi-state Phylogeny

NASA Astrophysics Data System (ADS)

Misra, Navodit; Blelloch, Guy; Ravi, R.; Schwartz, Russell

Accurate reconstruction of phylogenies remains a key challenge in evolutionary biology. Most biologically plausible formulations of the problem are formally NP-hard, with no known efficient solution. The standard in practice are fast heuristic methods that are empirically known to work very well in general, but can yield results arbitrarily far from optimal. Practical exact methods, which yield exponential worst-case running times but generally much better times in practice, provide an important alternative. We report progress in this direction by introducing a provably optimal method for the weighted multi-state maximum parsimony phylogeny problem. The method is based on generalizing the notion of the Buneman graph, a construction key to efficient exact methods for binary sequences, so as to apply to sequences with arbitrary finite numbers of states with arbitrary state transition weights. We implement an integer linear programming (ILP) method for the multi-state problem using this generalized Buneman graph and demonstrate that the resulting method is able to solve data sets that are intractable by prior exact methods in run times comparable with popular heuristics. Our work provides the first method for provably optimal maximum parsimony phylogeny inference that is practical for multi-state data sets of more than a few characters.

Catalytic-site design for inverse heavy-enzyme isotope effects in human purine nucleoside phosphorylase

PubMed Central

Harijan, Rajesh K.; Zoi, Ioanna; Antoniou, Dimitri; Schwartz, Steven D.; Schramm, Vern L.

2017-01-01

Heavy-enzyme isotope effects (15N-, 13C-, and 2H-labeled protein) explore mass-dependent vibrational modes linked to catalysis. Transition path-sampling (TPS) calculations have predicted femtosecond dynamic coupling at the catalytic site of human purine nucleoside phosphorylase (PNP). Coupling is observed in heavy PNPs, where slowed barrier crossing caused a normal heavy-enzyme isotope effect (kchem light/kchem heavy > 1.0). We used TPS to design mutant F159Y PNP, predicted to improve barrier crossing for heavy F159Y PNP, an attempt to generate a rare inverse heavy-enzyme isotope effect (kchem light/kchem heavy < 1.0). Steady-state kinetic comparison of light and heavy native PNPs to light and heavy F159Y PNPs revealed similar kinetic properties. Pre–steady-state chemistry was slowed 32-fold in F159Y PNP. Pre–steady-state chemistry compared heavy and light native and F159Y PNPs and found a normal heavy-enzyme isotope effect of 1.31 for native PNP and an inverse effect of 0.75 for F159Y PNP. Increased isotopic mass in F159Y PNP causes more efficient transition state formation. Independent validation of the inverse isotope effect for heavy F159Y PNP came from commitment to catalysis experiments. Most heavy enzymes demonstrate normal heavy-enzyme isotope effects, and F159Y PNP is a rare example of an inverse effect. Crystal structures and TPS dynamics of native and F159Y PNPs explore the catalytic-site geometry associated with these catalytic changes. Experimental validation of TPS predictions for barrier crossing establishes the connection of rapid protein dynamics and vibrational coupling to enzymatic transition state passage. PMID:28584087

Programmable superpositions of Ising configurations

NASA Astrophysics Data System (ADS)

Sieberer, Lukas M.; Lechner, Wolfgang

2018-05-01

We present a framework to prepare superpositions of bit strings, i.e., many-body spin configurations, with deterministic programmable probabilities. The spin configurations are encoded in the degenerate ground states of the lattice-gauge representation of an all-to-all connected Ising spin glass. The ground-state manifold is invariant under variations of the gauge degrees of freedom, which take the form of four-body parity constraints. Our framework makes use of these degrees of freedom by individually tuning them to dynamically prepare programmable superpositions. The dynamics combines an adiabatic protocol with controlled diabatic transitions. We derive an effective model that allows one to determine the control parameters efficiently even for large system sizes.

Bichromatic laser cooling in a three-level system

NASA Astrophysics Data System (ADS)

Gupta, R.; Xie, C.; Padua, S.; Batelaan, H.; Metcalf, H.

1993-11-01

We report a 1D study of optical forces on atoms in a two-frequency laser field. The light couples two ground state hyperfine structure levels to a common excited state of 85Rb, thus forming a Λ system. We observe a new type of sub-Doppler coupling with blue-tuned light that uses neither polarization gradients nor magnetic fields, efficient heating with red tuning, and the spatial phase dependence of these. We observed deflection from a rectified dipole force and determined its velocity dependence and capture range. We report velocity selective resonances associated with Raman transitions. A simplified semiclassical calculation agrees qualitatively with our measurements.

Spectroscopy of Rb{sub 2} dimers in solid {sup 4}He

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

Moroshkin, P.; Hofer, A.; Ulzega, S.

We present experimental and theoretical studies of the absorption, emission, and photodissociation spectra of Rb{sub 2} molecules in solid helium. We have identified 11 absorption bands of Rb{sub 2}. All laser-excited molecular states are quenched by the interaction with the He matrix. The quenching results in efficient population of a metastable (1) {sup 3}{pi}{sub u} state, which emits fluorescence at 1042 nm. In order to explain the fluorescence at the forbidden transition and its time dependence we propose a new molecular exciplex Rb{sub 2}({sup 3}{pi}{sub u})He{sub 2}. We have also found evidence for the formation of diatomic bubble states followingmore » photodissociation of Rb{sub 2}.« less

Suppression of Zeeman gradients by nuclear polarization in double quantum dots.

PubMed

Frolov, S M; Danon, J; Nadj-Perge, S; Zuo, K; van Tilburg, J W W; Pribiag, V S; van den Berg, J W G; Bakkers, E P A M; Kouwenhoven, L P

2012-12-07

We use electric dipole spin resonance to measure dynamic nuclear polarization in InAs nanowire quantum dots. The resonance shifts in frequency when the system transitions between metastable high and low current states, indicating the presence of nuclear polarization. We propose that the low and the high current states correspond to different total Zeeman energy gradients between the two quantum dots. In the low current state, dynamic nuclear polarization efficiently compensates the Zeeman gradient due to the g-factor mismatch, resulting in a suppressed total Zeeman gradient. We present a theoretical model of electron-nuclear feedback that demonstrates a fixed point in nuclear polarization for nearly equal Zeeman splittings in the two dots and predicts a narrowed hyperfine gradient distribution.

UAB UTC transit related activities

DOT National Transportation Integrated Search

2011-01-25

The ITS Strategic Plan outlines a strategy for improving the efficiency of the Region's existing highway and transit systems. The Region's overall goal is to improve the efficiency and effectiveness of existing systems so as to reduce the need to bui...

Performance measures to assess resiliency and efficiency of transit systems [research brief].

DOT National Transportation Integrated Search

2017-03-01

Transit agencies, like other transportation agencies, are interested in assessing the short-, mid-, and long-term performance of their infrastructure with the objectives of making better decisions that will enhance resiliency and efficiency. This rep...

High-resolution X-ray emission spectroscopy with transition-edge sensors: present performance and future potential

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

Uhlig, J.; Doriese, W. B.; Fowler, J. W.

2015-04-21

X-ray emission spectroscopy (XES) is a powerful element-selective tool to analyze the oxidation states of atoms in complex compounds, determine their electronic configuration, and identify unknown compounds in challenging environments. Until now the low efficiency of wavelength-dispersive X-ray spectrometer technology has limited the use of XES, especially in combination with weaker laboratory X-ray sources. More efficient energy-dispersive detectors have either insufficient energy resolution because of the statistical limits described by Fano or too low counting rates to be of practical use. This paper updates an approach to high-resolution X-ray emission spectroscopy that uses a microcalorimeter detector array of superconducting transition-edgemore » sensors (TESs). TES arrays are discussed and compared with conventional methods, and shown under which circumstances they are superior. It is also shown that a TES array can be integrated into a table-top time-resolved X-ray source and a soft X-ray synchrotron beamline to perform emission spectroscopy with good chemical sensitivity over a very wide range of energies.« less

Kinetic and radiative power from optically thin accretion flows

NASA Astrophysics Data System (ADS)

Sądowski, Aleksander; Gaspari, Massimo

2017-06-01

We perform a set of general relativistic, radiative, magneto-hydrodynamical simulations (GR-RMHD) to study the transition from radiatively inefficient to efficient state of accretion on a non-rotating black hole. We study ion to electron temperature ratios ranging from TI/Te = 10 to 100, and simulate flows corresponding to accretion rates as low as 10^{-6}\\dot{M}_Edd, and as high as 10^{-2}\\dot{M}_Edd. We have found that the radiative output of accretion flows increases with accretion rate, and that the transition occurs earlier for hotter electrons (lower TI/Te ratio). At the same time, the mechanical efficiency hardly changes and accounts to ≈3 per cent of the accreted rest mass energy flux, even at the highest simulated accretion rates. This is particularly important for the mechanical active galactic nuclei (AGN) feedback regulating massive galaxies, groups and clusters. Comparison with recent observations of radiative and mechanical AGN luminosities suggests that the ion to electron temperature ratio in the inner, collisionless accretion flow should fall within 10 < TI/Te < 30, I.e. the electron temperature should be several percent of the ion temperature.

Tradeoffs between costs and greenhouse gas emissions in the design of urban transit systems

NASA Astrophysics Data System (ADS)

Griswold, Julia B.; Madanat, Samer; Horvath, Arpad

2013-12-01

Recent investments in the transit sector to address greenhouse gas emissions have concentrated on purchasing efficient replacement vehicles and inducing mode shift from the private automobile. There has been little focus on the potential of network and operational improvements, such as changes in headways, route spacing, and stop spacing, to reduce transit emissions. Most models of transit system design consider user and agency cost while ignoring emissions and the potential environmental benefit of operational improvements. We use a model to evaluate the user and agency costs as well as greenhouse gas benefit of design and operational improvements to transit systems. We examine how the operational characteristics of urban transit systems affect both costs and greenhouse gas emissions. The research identifies the Pareto frontier for designing an idealized transit network. Modes considered include bus, bus rapid transit (BRT), light rail transit (LRT), and metro (heavy) rail, with cost and emissions parameters appropriate for the United States. Passenger demand follows a many-to-many travel pattern with uniformly distributed origins and destinations. The approaches described could be used to optimize the network design of existing bus service or help to select a mode and design attributes for a new transit system. The results show that BRT provides the lowest cost but not the lowest emissions for our large city scenarios. Bus and LRT systems have low costs and the lowest emissions for our small city scenarios. Relatively large reductions in emissions from the cost-optimal system can be achieved with only minor increases in user travel time.

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.

SparseMaps—A systematic infrastructure for reduced-scaling electronic structure methods. III. Linear-scaling multireference domain-based pair natural orbital N-electron valence perturbation theory

NASA Astrophysics Data System (ADS)

Guo, Yang; Sivalingam, Kantharuban; Valeev, Edward F.; Neese, Frank

2016-03-01

Multi-reference (MR) electronic structure methods, such as MR configuration interaction or MR perturbation theory, can provide reliable energies and properties for many molecular phenomena like bond breaking, excited states, transition states or magnetic properties of transition metal complexes and clusters. However, owing to their inherent complexity, most MR methods are still too computationally expensive for large systems. Therefore the development of more computationally attractive MR approaches is necessary to enable routine application for large-scale chemical systems. Among the state-of-the-art MR methods, second-order N-electron valence state perturbation theory (NEVPT2) is an efficient, size-consistent, and intruder-state-free method. However, there are still two important bottlenecks in practical applications of NEVPT2 to large systems: (a) the high computational cost of NEVPT2 for large molecules, even with moderate active spaces and (b) the prohibitive cost for treating large active spaces. In this work, we address problem (a) by developing a linear scaling "partially contracted" NEVPT2 method. This development uses the idea of domain-based local pair natural orbitals (DLPNOs) to form a highly efficient algorithm. As shown previously in the framework of single-reference methods, the DLPNO concept leads to an enormous reduction in computational effort while at the same time providing high accuracy (approaching 99.9% of the correlation energy), robustness, and black-box character. In the DLPNO approach, the virtual space is spanned by pair natural orbitals that are expanded in terms of projected atomic orbitals in large orbital domains, while the inactive space is spanned by localized orbitals. The active orbitals are left untouched. Our implementation features a highly efficient "electron pair prescreening" that skips the negligible inactive pairs. The surviving pairs are treated using the partially contracted NEVPT2 formalism. A detailed comparison between the partial and strong contraction schemes is made, with conclusions that discourage the strong contraction scheme as a basis for local correlation methods due to its non-invariance with respect to rotations in the inactive and external subspaces. A minimal set of conservatively chosen truncation thresholds controls the accuracy of the method. With the default thresholds, about 99.9% of the canonical partially contracted NEVPT2 correlation energy is recovered while the crossover of the computational cost with the already very efficient canonical method occurs reasonably early; in linear chain type compounds at a chain length of around 80 atoms. Calculations are reported for systems with more than 300 atoms and 5400 basis functions.

Governance of urban transitions: towards sustainable resource efficient urban infrastructures

NASA Astrophysics Data System (ADS)

Swilling, Mark; Hajer, Maarten

2017-12-01

The transition to sustainable resource efficient cities calls for new governance arrangements. The awareness that the doubling of the global urban population will result in unsustainable levels of demand for natural resources requires changes in the existing socio-technical systems. Domestic material consumption could go up from 40 billion tons in 2010, to 89 billion tons by 2050. While there are a number of socio-technical alternatives that could result in significant improvements in the resource efficiency of urban systems in developed and developing countries (specifically bus-rapid transit, district energy systems and green buildings), we need to rethink the urban governance arrangements to get to this alternative pathway. We note modes of urban governance have changed over the past century as economic and urban development paradigms have shifted at the national and global levels. This time round we identify cities as leading actors in the transition to more sustainable modes of production and consumption as articulated in the Sustainable Development Goals. This has resulted in a surge of urban experimentation across all world regions, both North and South. Building on this empirically observable trend we suggest this can also be seen as a building block of a new urban governance paradigm. An ‘entrepreneurial urban governance’ is proposed that envisages an active and goal-setting role for the state, but in ways that allows broader coalitions of urban ‘agents of change’ to emerge. This entrepreneurial urban governance fosters and promotes experimentation rather than suppressing the myriad of such initiatives across the globe, and connects to global city networks for systemic learning between cities. Experimentation needs to result in a contextually appropriate balance between economic, social, technological and sustainable development. A full and detailed elaboration of the arguments and sources for this article can be found in chapter 6 of Swilling M et al 2017 Resource Requirements of Future Urbanization (Paris: International Resource Panel).

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

A new phosphine oxide host based on ortho-disubstituted dibenzofuran for efficient electrophosphorescence: towards high triplet state excited levels and excellent thermal, morphological and efficiency stability.

PubMed

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

2011-08-01

An efficient host for blue and green electrophosphorescence, 4,6-bis(diphenylphosphoryl)dibenzofuran (o-DBFDPO), with the structure of a short-axis-substituted dibenzofuran was designed and synthesised. It appears that the greater density of the diphenylphosphine oxide (DPPO) moieties in the short-axis substitution configuration effectively restrains the intermolecular interactions, because only very weak π-π stacking interactions could be observed, with a centroid-to-centroid distance of 3.960 Å. The improved thermal stability of o-DBFDPO was corroborated by its very high glass transition temperature (T(g)) of 191 °C, which is the result of the symmetric disubstitution structure. Photophysical investigation showed o-DBFDPO to be superior to the monosubstituted derivative, with a longer lifetime (1.95 ns) and a higher photoluminescent quantum efficiency (61 %). The lower first singlet state excited level (3.63 eV) of o-DBFDPO demonstrates the stronger polarisation effect attributable to the greater number of DPPO moieties. Simultaneously, an extremely high first triplet state excited level (T(1)) of 3.16 eV is observed, demonstrating the tiny influence of short-axis substitution on T(1). The improved carrier injection ability, which contributed to low driving voltages of blue- and green-emitting phosphorescent organic light-emitting diodes (PHOLEDs), was further confirmed by Gaussian calculation. Furthermore, the better thermal and morphological properties of o-DBFDPO and the matched frontier molecular orbital (FMO) levels in the devices significantly reduced efficiency roll-offs. Efficient blue and green electrophosphorescence based on the o-DBFDPO host was demonstrated. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

11% efficiency solid-state dye-sensitized solar cells with copper(II/I) hole transport materials

PubMed Central

Cao, Yiming; Saygili, Yasemin; Ummadisingu, Amita; Teuscher, Joël; Luo, Jingshan; Pellet, Norman; Giordano, Fabrizio; Zakeeruddin, Shaik Mohammed; Moser, Jacques -E.; Freitag, Marina; Hagfeldt, Anders; Grätzel, Michael

2017-01-01

Solid-state dye-sensitized solar cells currently suffer from issues such as inadequate nanopore filling, low conductivity and crystallization of hole-transport materials infiltrated in the mesoscopic TiO2 scaffolds, leading to low performances. Here we report a record 11% stable solid-state dye-sensitized solar cell under standard air mass 1.5 global using a hole-transport material composed of a blend of [Cu (4,4′,6,6′-tetramethyl-2,2′-bipyridine)2](bis(trifluoromethylsulfonyl)imide)2 and [Cu (4,4′,6,6′-tetramethyl-2,2′-bipyridine)2](bis(trifluoromethylsulfonyl)imide). The amorphous Cu(II/I) conductors that conduct holes by rapid hopping infiltrated in a 6.5 μm-thick mesoscopic TiO2 scaffold are crucial for achieving such high efficiency. Using time-resolved laser photolysis, we determine the time constants for electron injection from the photoexcited sensitizers Y123 into the TiO2 and regeneration of the Y123 by Cu(I) to be 25 ps and 3.2 μs, respectively. Our work will foster the development of low-cost solid-state photovoltaic based on transition metal complexes as hole conductors. PMID:28598436

Laser properties of Fe2+:ZnSe fabricated by solid-state diffusion bonding

NASA Astrophysics Data System (ADS)

Balabanov, S. S.; Firsov, K. N.; Gavrishchuk, E. M.; Ikonnikov, V. B.; Kazantsev, S. Yu; Kononov, I. G.; Kotereva, T. V.; Savin, D. V.; Timofeeva, N. A.

2018-04-01

The characteristics of an Fe2+:ZnSe laser at room temperature and its active elements with undoped faces were studied. Polycrystalline elements with one or two diffusion-doped internal layers were obtained by the solid-state diffusion bonding technique applied to chemical vapor deposition grown ZnSe plates preliminary doped with Fe2+ ions in the process of hot isostatic pressing. A non-chain electric-discharge HF laser was used to pump the crystals. It was demonstrated that increasing the number of doped layers allows increasing the maximum diameter of the pump radiation spot and the pump energy without the appearance of transversal parasitic oscillation. For the two-layer-doped active element with a diameter of 20 mm an output energy of 480 mJ was achieved with 37% total efficiency with respect to the absorbed energy. The obtained results demonstrate the potential of the developed technology for fabrication of active elements by the solid-state diffusion bonding technique combined with the hot isostatic pressing treatment for efficient IR lasers based on chalcogenides doped with transition metal ions.

Two-Dimensional Electronic Spectroscopy of Benzene, Phenol, and Their Dimer: An Efficient First-Principles Simulation Protocol.

PubMed

Nenov, Artur; Mukamel, Shaul; Garavelli, Marco; Rivalta, Ivan

2015-08-11

First-principles simulations of two-dimensional electronic spectroscopy in the ultraviolet region (2DUV) require computationally demanding multiconfigurational approaches that can resolve doubly excited and charge transfer states, the spectroscopic fingerprints of coupled UV-active chromophores. Here, we propose an efficient approach to reduce the computational cost of accurate simulations of 2DUV spectra of benzene, phenol, and their dimer (i.e., the minimal models for studying electronic coupling of UV-chromophores in proteins). We first establish the multiconfigurational recipe with the highest accuracy by comparison with experimental data, providing reference gas-phase transition energies and dipole moments that can be used to construct exciton Hamiltonians involving high-lying excited states. We show that by reducing the active spaces and the number of configuration state functions within restricted active space schemes, the computational cost can be significantly decreased without loss of accuracy in predicting 2DUV spectra. The proposed recipe has been successfully tested on a realistic model proteic system in water. Accounting for line broadening due to thermal and solvent-induced fluctuations allows for direct comparison with experiments.

Narrow Energy Gap between Triplet and Singlet Excited States of Sn2+ in Borate Glass

PubMed Central

Masai, Hirokazu; Yamada, Yasuhiro; Suzuki, Yuto; Teramura, Kentaro; Kanemitsu, Yoshihiko; Yoko, Toshinobu

2013-01-01

Transparent inorganic luminescent materials have attracted considerable scientific and industrial attention recently because of their high chemical durability and formability. However, photoluminescence dynamics of ns2-type ions in oxide glasses has not been well examined, even though they can exhibit high quantum efficiency. We report on the emission property of Sn2+-doped strontium borate glasses. Photoluminescence dynamics studies show that the peak energy of the emission spectrum changes with time because of site distribution of emission centre in glass. It is also found that the emission decay of the present glass consists of two processes: a faster S1-S0 transition and a slower T1-S0 relaxation, and also that the energy difference between T1 and S1 states was found to be much smaller than that of (Sn, Sr)B6O10 crystals. We emphasize that the narrow energy gap between the S1 and T1 states provides the glass phosphor a high quantum efficiency, comparable to commercial crystalline phosphors. PMID:24345869

A dianionic phosphorane intermediate and transition states in an associative A(N)+D(N) mechanism for the ribonucleaseA hydrolysis reaction.

PubMed

Elsässer, Brigitta; Valiev, Marat; Weare, John H

2009-03-25

The RNaseA enzyme efficiently cleaves phosphodiester bonds in the RNA backbone. Phosphoryl transfer plays a central role in many biochemical reactions, and this is one of the most studied enzymes. However, there remains considerable controversy about the reaction mechanism. Most of this debate centers around the roles of the conserved residues, structures of the transition state or states, the possibility of a stable intermediate, and the charge and structure of this intermediate. In this communication we report calculations of the mechanism of the hydrolysis step in this reaction using a comprehensive QM/MM theoretical approach that includes a high level calculation of the interactions in the QM region, free energy estimates along an NEB optimized reaction path, and the inclusion of the interaction of the protein surroundings and solvent. Contrary to prior calculations we find a stable pentacoordinated dianionic phosphorane intermediate in the reaction path supporting an A(N)+D(N) reaction mechanism. In the transition state in the path from the reactant to the intermediate state (with barrier of 3.96 kcal/mol and intermediate stability of 2.21 kcal/mol) a proton from the attacking water is partially transferred to the His119 residue and the PO bond only partially formed from the remaining nucleophilic OH(-) species (bond order (BO) 0.11). In passing from the intermediate to the product state (barrier 13.22 kcal/mol) the PO bond on the cyclic phosphorane intermediate is nearly broken (BO 0.28) and the transfer of the proton from the Lys41 is almost complete (Lys41-H BO 0.87). In the product state a proton has been transferred from Lys41 to the O2' position of the sugar. The role of Lys41 as the catalytic acid is a result of the relative positioning of the Lys41 and His12 in the catalytic site. This configuration is supported by calculations and docking studies.

Cooperativity and pseudo-cooperativity in the glutathione S-transferase from Plasmodium falciparum.

PubMed

Liebau, Eva; De Maria, Francesca; Burmeister, Cora; Perbandt, Markus; Turella, Paola; Antonini, Giovanni; Federici, Giorgio; Giansanti, Francesco; Stella, Lorenzo; Lo Bello, Mario; Caccuri, Anna Maria; Ricci, Giorgio

2005-07-15

Binding and catalytic properties of glutathione S-transferase from Plasmodium falciparum (PfGST) have been studied by means of fluorescence, steady state and pre-steady state kinetic experiments, and docking simulations. This enzyme displays a peculiar reversible low-high affinity transition, never observed in other GSTs, which involves the G-site and shifts the apparent K(D) for glutathione (GSH) from 200 to 0.18 mM. The transition toward the high affinity conformation is triggered by the simultaneous binding of two GSH molecules to the dimeric enzyme, and it is manifested as an uncorrected homotropic behavior, termed "pseudo-cooperativity." The high affinity enzyme is able to activate GSH, lowering its pK(a) value from 9.0 to 7.0, a behavior similar to that found in all known GSTs. Using 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole, this enzyme reveals a potential optimized mechanism for the GSH conjugation but a low catalytic efficiency mainly due to a very low affinity for this co-substrate. Conversely, PfGST efficiently binds one molecule of hemin/monomer. The binding is highly cooperative (n(H) = 1.8) and occurs only when GSH is bound to the enzyme. The thiolate of GSH plays a crucial role in the intersubunit communication because no cooperativity is observed when S-methylglutathione replaces GSH. Docking simulations suggest that hemin binds to a pocket leaning into both the G-site and the H-site. The iron is coordinated by the amidic nitrogen of Asn-115, and the two carboxylate groups are in electrostatic interaction with the epsilon-amino group of Lys-15. Kinetic and structural data suggest that PfGST evolved by optimizing its binding property with the parasitotoxic hemin rather than its catalytic efficiency toward toxic electrophilic compounds.

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.

Anderson metal-insulator transitions with classical magnetic impurities

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

Jung, Daniel; Kettemann, Stefan

We study the effects of classical magnetic impurities on the Anderson metal-insulator transition (AMIT) numerically. In particular we find that while a finite concentration of Ising impurities lowers the critical value of the site-diagonal disorder amplitude W{sub c}, in the presence of Heisenberg impurities, W{sub c} is first increased with increasing exchange coupling strength J due to time-reversal symmetry breaking. The resulting scaling with J is compared to analytical predictions by Wegner [1]. The results are obtained numerically, based on a finite-size scaling procedure for the typical density of states [2], which is the geometric average of the local densitymore » of states. The latter can efficiently be calculated using the kernel polynomial method [3]. Although still suffering from methodical shortcomings, our method proves to deliver results close to established results for the orthogonal symmetry class [4]. We extend previous approaches [5] by combining the KPM with a finite-size scaling analysis. We also discuss the relevance of our findings for systems like phosphor-doped silicon (Si:P), which are known to exhibit a quantum phase transition from metal to insulator driven by the interplay of both interaction and disorder, accompanied by the presence of a finite concentration of magnetic moments [6].« less

2014 Summer Series - Mark Jacobson - Roadmaps for Transitioning All 50 US States to Wind, Water and Solar Power

NASA Image and Video Library

2014-07-08

Global warming, air pollution, and energy insecurity are three of the most significant problems facing the world today. This talk discusses the development of technical and economic plans to convert the energy infrastructure of each of the 50 United States to those powered by 100% wind, water, and sunlight (WWS) for all purposes, namely electricity, transportation, industry, and heating/cooling, after energy efficiency measures have been accounted for. The plans call for all new energy to be WWS by 2020, ~80% conversion of existing energy by 2030, and 100% by 2050 through aggressive policy measures and natural transition. Resource availability, footprint and spacing areas required, jobs created, energy costs, avoided costs from air pollution mortality and morbidity and climate damage, methods of ensuring reliability of the grid, and impacts of offshore wind farms on hurricane dissipation are discussed. Air pollution reductions alone due to the plan would eliminate ~60,000 U.S. premature mortalities, avoiding costs equivalent to 3.2% of the United States GDP. Climate cost reductions are of similar order. The plans stabilize energy prices because fuel costs are zero.

Ballistic induced pumping of hypersonic heat current in DNA nano wire

NASA Astrophysics Data System (ADS)

Behnia, Sohrab; Panahinia, Robabe

2016-12-01

Heat shuttling properties of DNA nano-wire driven by an external force against the spontaneous heat current direction in non-zero temperature bias (non averaged) have been studied. We examined the valid region of driving amplitude and frequency to have pumping state in terms of temperature bias and the system size. It was shown that DNA could act as a high efficiency thermal pump in the hypersonic region. Amplitude-dependent resonance frequencies of DNA indicating intrinsic base pair internal vibrations have been detected. Nonlinearity implies that by increasing the driven amplitude new vibration modes are detected. To verify the results, an analytical parallel investigation based on multifractal concept has been done. By using the geometric properties of the strange attractor of the system, the threshold value to transition to the pumping state for given external amplitude has been identified. It was shown that the system undergoes a phase transition in sliding point to the pumping state. Fractal dimension demonstrates that the ballistic transport is responsible for energy pumping in the system. In the forbidden band gap, DNA could transmit the energy by exceeding the threshold amplitude. Despite of success in energy pumping, in this framework, DNA could not act as a real cooler.

Experimental and computational analysis of the transition state for ribonuclease A-catalyzed RNA 2′-O-transphosphorylation

PubMed Central

Gu, Hong; Zhang, Shuming; Wong, Kin-Yiu; Radak, Brian K.; Dissanayake, Thakshila; Kellerman, Daniel L.; Dai, Qing; Miyagi, Masaru; Anderson, Vernon E.; York, Darrin M.; Piccirilli, Joseph A.; Harris, Michael E.

2013-01-01

Enzymes function by stabilizing reaction transition states; therefore, comparison of the transition states of enzymatic and nonenzymatic model reactions can provide insight into biological catalysis. Catalysis of RNA 2′-O-transphosphorylation by ribonuclease A is proposed to involve electrostatic stabilization and acid/base catalysis, although the structure of the rate-limiting transition state is uncertain. Here, we describe coordinated kinetic isotope effect (KIE) analyses, molecular dynamics simulations, and quantum mechanical calculations to model the transition state and mechanism of RNase A. Comparison of the 18O KIEs on the 2′O nucleophile, 5′O leaving group, and nonbridging phosphoryl oxygens for RNase A to values observed for hydronium- or hydroxide-catalyzed reactions indicate a late anionic transition state. Molecular dynamics simulations using an anionic phosphorane transition state mimic suggest that H-bonding by protonated His12 and Lys41 stabilizes the transition state by neutralizing the negative charge on the nonbridging phosphoryl oxygens. Quantum mechanical calculations consistent with the experimental KIEs indicate that expulsion of the 5′O remains an integral feature of the rate-limiting step both on and off the enzyme. Electrostatic interactions with positively charged amino acid site chains (His12/Lys41), together with proton transfer from His119, render departure of the 5′O less advanced compared with the solution reaction and stabilize charge buildup in the transition state. The ability to obtain a chemically detailed description of 2′-O-transphosphorylation transition states provides an opportunity to advance our understanding of biological catalysis significantly by determining how the catalytic modes and active site environments of phosphoryl transferases influence transition state structure. PMID:23878223

Theoretical study on the low-lying excited states of the phosphorus monoiodide (PI) including the spin-orbit coupling

NASA Astrophysics Data System (ADS)

Zhang, Xiaomei; Liu, Xiaoting; Liang, Guiying; Li, Rui; Xu, Haifeng; Yan, Bing

2016-01-01

The potential energy curves (PECs) of the 22 Λ-S states of the phosphorus monoiodide (PI) molecule have been calculated at the level of MRCI+Q method with correlation-consistent quadruple-ζ quality basis set. The spectroscopic constants of the bound states are determined, which well reproduce the available measurements. The metastable a1Δ state has been reported for the first time, which lies between the X3Σ- and b1Σ+ states and have much deeper well than the ground state. The R-dependent spin-orbit (SO) matrix elements are calculated with the full-electron Breit-Pauli operator. Based on the SO matrix elements, the perturbations that the 23Π state may suffer from are analyzed in detail. The SOC effect makes the original Λ-S states split into 51 Ω states. In the zero-field splitting of the ground state X3Σ-, the spin-spin coupling contribution (2.23 cm-1) is found to be much smaller compared to the spin-orbit coupling contribution (50 cm-1). The avoided crossings between the Ω states lead to much shallower potential wells and the change of dissociation relationships of the states. The Ω-state wavefunctions are analyzed depending on their Λ-S compositions, showing the strong interactions among several quasidegenerate Λ-S states of the same total SO symmetry. The transition properties including electric dipole (E1), magnetic dipole (M1), and electric quadrupole (E2) transition moments (TMs), the Franck-Condon factors, the transition probabilities and the radiative lifetimes are computed for the transitions between Ω components of a1Δ and b1Σ+ states and ground state. The transition probabilities induced by the E1, E2, and M1 transitions are evaluated. The E2 makes little effect on transition probabilities. In contrast, the E1 transition makes the main contribution to the transition probability and the M1 transition also brings the influence that cannot be neglected. Finally, the radiative lifetimes are determined with the transition moments including E1 and M1. The lifetime of transition (2)0+-X10+ is evaluated at the level of millisecond, much smaller than that of the transition (2)0+-X21.

The kinetics of effector binding to phosphofructokinase. The allosteric conformational transition induced by 1,N6-ethenoadenosine triphosphate.

PubMed Central

Roberts, D; Kellett, G L

1979-01-01

1. The fluorescent ATP analogue 1,N6-etheno-ATP is a good substrate and an efficient allosteric inhibitor of rabbit skeletal-muscle phosphofructokinase. 2. Fluorescence energy transfer occurs between bound 1,N6-etheno-ATP and phosphofructokinase. 1,N6-Etheno-ATP fluorescence is enhanced, intrinsic protein fluorescence is quenched, and the excitation spectrum of 1,N6-etheno-ATP fluorescence is characteristic of protein absorption. 3. The binding reaction of 1,N6-etheno-ATP observed by stopped-flow fluorimetry is biphasic. The fast phase results from binding to the catalytic site alone. The slow phase results from the allosteric transition of the R conformation into the T conformation induced by the binding of 1,N6-etheno-ATP to the regulatory site. 4. The fluorescence signal that allows the transition of the R conformation into the T conformation to be observed does not arise from 1,N6-etheno-ATP bound to the regulatory site. It arises instead from 1,N6-etheno-ATP bound to the catalytic site as a consequence of changes at the catalytic site caused by the transition of the R conformation into the T conformation. 5. In the presence of excess of Mg2+, the affinity of 1,N6-etheno-ATP for the regulatory site is very much greater in the T state than in the R state. Images Fig. 5. Fig. 8. PMID:160791

Optimization by infusion of multiple reaction monitoring transitions for sensitive quantification of peptides by liquid chromatography/mass spectrometry.

PubMed

Alghanem, Bandar; Nikitin, Frédéric; Stricker, Thomas; Duchoslav, Eva; Luban, Jeremy; Strambio-De-Castillia, Caterina; Muller, Markus; Lisacek, Frédérique; Varesio, Emmanuel; Hopfgartner, Gérard

2017-05-15

In peptide quantification by liquid chromatography/mass spectrometry (LC/MS), the optimization of multiple reaction monitoring (MRM) parameters is essential for sensitive detection. We have compared different approaches to build MRM assays, based either on flow injection analysis (FIA) of isotopically labelled peptides, or on the knowledge and the prediction of the best settings for MRM transitions and collision energies (CE). In this context, we introduce MRMOptimizer, an open-source software tool that processes spectra and assists the user in selecting transitions in the FIA workflow. MS/MS spectral libraries with CE voltages from 10 to 70 V are automatically acquired in FIA mode for isotopically labelled peptides. Then MRMOptimizer determines the optimal MRM settings for each peptide. To assess the quantitative performance of our approach, 155 peptides, representing 84 proteins, were analysed by LC/MRM-MS and the peak areas were compared between: (A) the MRMOptimizer-based workflow, (B1) the SRMAtlas transitions set used 'as-is'; (B2) the same SRMAtlas set with CE parameters optimized by Skyline. 51% of the three most intense transitions per peptide were shown to be common to both A and B1/B2 methods, and displayed similar sensitivity and peak area distributions. The peak areas obtained with MRMOptimizer for transitions sharing either the precursor ion charge state or the fragment ions with the SRMAtlas set at unique transitions were increased 1.8- to 2.3-fold. The gain in sensitivity using MRMOptimizer for transitions with different precursor ion charge state and fragment ions (8% of the total), reaches a ~ 11-fold increase. Isotopically labelled peptides can be used to optimize MRM transitions more efficiently in FIA than by searching databases. The MRMOptimizer software is MS independent and enables the post-acquisition selection of MRM parameters. Coefficients of variation for optimal CE values are lower than those obtained with the SRMAtlas approach (B2) and one additional peptide was detected. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Unexpectedly Fast Phonon-Assisted Exciton Hopping between Carbon Nanotubes

DOE PAGES

Davoody, A. H.; Karimi, F.; Arnold, M. S.; ...

2017-06-05

Carbon-nanotube (CNT) aggregates are promising light-absorbing materials for photovoltaics. The hopping rate of excitons between CNTs directly affects the efficiency of these devices. We theoretically investigate phonon-assisted exciton hopping, where excitons scatter with phonons into a same-tube transition state, followed by intertube Coulomb scattering into the final state. Second-order hopping between bright excitonic states is as fast as the first-order process (~1 ps). For perpendicular CNTs, the high rate stems from the high density of phononic states; for parallel CNTs, the reason lies in relaxed selection rules. Moreover, second-order exciton transfer between dark and bright states, facilitated by phonons withmore » large angular momentum, has rates comparable to bright-to-bright transfer, so dark excitons provide an additional pathway for energy transfer in CNT composites. Furthermore, as dark excitons are difficult to probe in experiment, predictive theory is critical for understanding exciton dynamics in CNT composites.« less

Unexpectedly Fast Phonon-Assisted Exciton Hopping between Carbon Nanotubes

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

Davoody, A. H.; Karimi, F.; Arnold, M. S.

Carbon-nanotube (CNT) aggregates are promising light-absorbing materials for photovoltaics. The hopping rate of excitons between CNTs directly affects the efficiency of these devices. We theoretically investigate phonon-assisted exciton hopping, where excitons scatter with phonons into a same-tube transition state, followed by intertube Coulomb scattering into the final state. Second-order hopping between bright excitonic states is as fast as the first-order process (~1 ps). For perpendicular CNTs, the high rate stems from the high density of phononic states; for parallel CNTs, the reason lies in relaxed selection rules. Moreover, second-order exciton transfer between dark and bright states, facilitated by phonons withmore » large angular momentum, has rates comparable to bright-to-bright transfer, so dark excitons provide an additional pathway for energy transfer in CNT composites. Furthermore, as dark excitons are difficult to probe in experiment, predictive theory is critical for understanding exciton dynamics in CNT composites.« less

Three-dimensional modeling, estimation, and fault diagnosis of spacecraft air contaminants.

PubMed

Narayan, A P; Ramirez, W F

1998-01-01

A description is given of the design and implementation of a method to track the presence of air contaminants aboard a spacecraft using an accurate physical model and of a procedure that would raise alarms when certain tolerance levels are exceeded. Because our objective is to monitor the contaminants in real time, we make use of a state estimation procedure that filters measurements from a sensor system and arrives at an optimal estimate of the state of the system. The model essentially consists of a convection-diffusion equation in three dimensions, solved implicitly using the principle of operator splitting, and uses a flowfield obtained by the solution of the Navier-Stokes equations for the cabin geometry, assuming steady-state conditions. A novel implicit Kalman filter has been used for fault detection, a procedure that is an efficient way to track the state of the system and that uses the sparse nature of the state transition matrices.

Complete protein-protein association kinetics in atomic detail revealed by molecular dynamics simulations and Markov modelling

NASA Astrophysics Data System (ADS)

Plattner, Nuria; Doerr, Stefan; de Fabritiis, Gianni; Noé, Frank

2017-10-01

Protein-protein association is fundamental to many life processes. However, a microscopic model describing the structures and kinetics during association and dissociation is lacking on account of the long lifetimes of associated states, which have prevented efficient sampling by direct molecular dynamics (MD) simulations. Here we demonstrate protein-protein association and dissociation in atomistic resolution for the ribonuclease barnase and its inhibitor barstar by combining adaptive high-throughput MD simulations and hidden Markov modelling. The model reveals experimentally consistent intermediate structures, energetics and kinetics on timescales from microseconds to hours. A variety of flexibly attached intermediates and misbound states funnel down to a transition state and a native basin consisting of the loosely bound near-native state and the tightly bound crystallographic state. These results offer a deeper level of insight into macromolecular recognition and our approach opens the door for understanding and manipulating a wide range of macromolecular association processes.

Fuzzy State Transition and Kalman Filter Applied in Short-Term Traffic Flow Forecasting

PubMed Central

Ming-jun, Deng; Shi-ru, Qu

2015-01-01

Traffic flow is widely recognized as an important parameter for road traffic state forecasting. Fuzzy state transform and Kalman filter (KF) have been applied in this field separately. But the studies show that the former method has good performance on the trend forecasting of traffic state variation but always involves several numerical errors. The latter model is good at numerical forecasting but is deficient in the expression of time hysteretically. This paper proposed an approach that combining fuzzy state transform and KF forecasting model. In considering the advantage of the two models, a weight combination model is proposed. The minimum of the sum forecasting error squared is regarded as a goal in optimizing the combined weight dynamically. Real detection data are used to test the efficiency. Results indicate that the method has a good performance in terms of short-term traffic forecasting. PMID:26779258

Disordered configurations of the Glauber model in two-dimensional networks

NASA Astrophysics Data System (ADS)

Bačić, Iva; Franović, Igor; Perc, Matjaž

2017-12-01

We analyze the ordering efficiency and the structure of disordered configurations for the zero-temperature Glauber model on Watts-Strogatz networks obtained by rewiring 2D regular square lattices. In the small-world regime, the dynamics fails to reach the ordered state in the thermodynamic limit. Due to the interplay of the perturbed regular topology and the energy neutral stochastic state transitions, the stationary state consists of two intertwined domains, manifested as multiclustered states on the original lattice. Moreover, for intermediate rewiring probabilities, one finds an additional source of disorder due to the low connectivity degree, which gives rise to small isolated droplets of spins. We also examine the ordering process in paradigmatic two-layer networks with heterogeneous rewiring probabilities. Comparing the cases of a multiplex network and the corresponding network with random inter-layer connectivity, we demonstrate that the character of the final state qualitatively depends on the type of inter-layer connections.

Fuzzy State Transition and Kalman Filter Applied in Short-Term Traffic Flow Forecasting.

PubMed

Deng, Ming-jun; Qu, Shi-ru

2015-01-01

Traffic flow is widely recognized as an important parameter for road traffic state forecasting. Fuzzy state transform and Kalman filter (KF) have been applied in this field separately. But the studies show that the former method has good performance on the trend forecasting of traffic state variation but always involves several numerical errors. The latter model is good at numerical forecasting but is deficient in the expression of time hysteretically. This paper proposed an approach that combining fuzzy state transform and KF forecasting model. In considering the advantage of the two models, a weight combination model is proposed. The minimum of the sum forecasting error squared is regarded as a goal in optimizing the combined weight dynamically. Real detection data are used to test the efficiency. Results indicate that the method has a good performance in terms of short-term traffic forecasting.

Preparation, Characterization and Application of Optical Switch Probes.

PubMed

Petchprayoon, Chutima; Marriott, Gerard

2010-08-01

Optical switches represent a new class of molecular probe with applications in high contrast imaging and optical manipulation of protein interactions. Small molecule, organic optical switches based on nitrospirobenzopyran (NitroBIPS) and their reactive derivatives and conjugates undergo efficient, rapid and reversible, orthogonal optically-driven transitions between a colorless spiro (SP) state and a colored merocyanine (MC) state. The excited MC-state also emits fluorescence, which serves as readout of the state of the switch. Defined optical perturbations of SP and MC generate a defined waveform of MC-fluorescence that can be isolated against unmodulated background signals by using a digital optical lock-in detection approach or to control specific dipolar interactions on proteins. The protocols describe general procedures for the synthesis and spectroscopic characterization of NitroBIPS and specifically labeled conjugates along with methods for the manipulation of dipolar interactions on proteins and imaging of the MC-state of NitroBIPS within living cells.

Microwave-based reaction screening: tandem retro-Diels-Alder/Diels-Alder cycloadditions of o-quinol dimers.

PubMed

Dong, Suwei; Cahill, Katharine J; Kang, Moon-Il; Colburn, Nancy H; Henrich, Curtis J; Wilson, Jennifer A; Beutler, John A; Johnson, Richard P; Porco, John A

2011-11-04

We have accomplished a parallel screen of cycloaddition partners for o-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of o-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of o-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor.

Reversible optical control of cyanine fluorescence in fixed and living cells: optical lock-in detection immunofluorescence imaging microscopy

PubMed Central

Yan, Yuling; Petchprayoon, Chutima; Mao, Shu; Marriott, Gerard

2013-01-01

Optical switch probes undergo rapid and reversible transitions between two distinct states, one of which may fluoresce. This class of probe is used in various super-resolution imaging techniques and in the high-contrast imaging technique of optical lock-in detection (OLID) microscopy. Here, we introduce optimized optical switches for studies in living cells under standard conditions of cell culture. In particular, a highly fluorescent cyanine probe (Cy or Cy3) is directly or indirectly linked to naphthoxazine (NISO), a highly efficient optical switch that undergoes robust, 405/532 nm-driven transitions between a colourless spiro (SP) state and a colourful merocyanine (MC) state. The intensity of Cy fluorescence in these Cy/Cy3-NISO probes is reversibly modulated between a low and high value in SP and MC states, respectively, as a result of Förster resonance energy transfer. Cy/Cy3-NISO probes are targeted to specific proteins in living cells where defined waveforms of Cy3 fluorescence are generated by optical switching of the SP and MC states. Finally, we introduce a new imaging technique (called OLID-immunofluorescence microscopy) that combines optical modulation of Cy3 fluorescence from Cy3/NISO co-labelled antibodies within fixed cells and OLID analysis to significantly improve image contrast in samples having high background or rare antigens. PMID:23267183

Energy efficient engine, low-pressure turbine boundary layer program

NASA Technical Reports Server (NTRS)

Gardner, W. B.

1981-01-01

A study was conducted to investigate development of boundary layers under the influence of velocity distributions simulating the suction side of two state-of-the-art turbine airfoils: a forward loaded airfoil (squared-off design) and an aft loaded airfoil (aft-loaded design). These velocity distributions were simulated in a boundary layer wind tunnel. Detailed measurements of boundary layer mean velocity and turbulence intensity profiles were obtained for an inlet turbulence level of 2.4 percent and an exit Reynolds number of 800,000. Flush-mounted hot film probes identified the boundary layer transition regimes in the adverse pressure gradient regions for both velocity distributions. Wall intermittency data showed good agreement with the correlations of Dhawan and Narasimha for the intermittency factor distribution in transitional flow regimes.

Using instability to reconfigure smart structures in a spring-mass model

NASA Astrophysics Data System (ADS)

Zhang, Jiaying; McInnes, Colin R.

2017-07-01

Multistable phenomenon have long been used in mechanism design. In this paper a subset of unstable configurations of a smart structure model will be used to develop energy-efficient schemes to reconfigure the structure. This new concept for reconfiguration uses heteroclinic connections to transition the structure between different unstable equal-energy states. In an ideal structure model zero net energy input is required for the reconfiguration, compared to transitions between stable equilibria across a potential barrier. A simple smart structure model is firstly used to identify sets of equal-energy unstable configurations using dynamical systems theory. Dissipation is then added to be more representative of a practical structure. A range of strategies are then used to reconfigure the smart structure using heteroclinic connections with different approaches to handle dissipation.

Thermal and fragility studies on microwave synthesized K2O-B2O3-V2O5 glasses

NASA Astrophysics Data System (ADS)

Harikamalasree, Reddy, M. Sudhakara; Viswanatha, R.; Reddy, C. Narayana

2016-05-01

Glasses with composition xK2O-60B2O3-(40-x) V2O5 (15 ≤ x ≤ 39 mol %) was prepared by an energy efficient microwave method. The heat capacity change (ΔCp) at glass transition (Tg), width of glass transition (ΔTg), heat capacities in the glassy (Cpg) and liquid (Cpl) state for the investigated glasses were extracted from Modulated Differential Scanning Calorimetry (MDSC) thermograms. The width of glass transition is less than 30°C, indicating that these glasses belongs to fragile category. Fragility functions [NBO]/(Vm3Tg) and (ΔCp/Cpl)increases with increasing modifier oxide concentration. Increase in fragility is attributed to the increasing coordination of boron. Further, addition of K2O creates NBOs and the flow mechanism involves bond switching between BOs and NBOs. Physical properties exhibit compositional dependence and these properties increase with increasing K2O concentration. The observed variations are qualitatively analyzed.

Molybdenum Carbamate Nanosheets as a New Class of Potential Phase Change Materials.

PubMed

Zhukovskyi, Maksym; Plashnitsa, Vladimir; Petchsang, Nattasamon; Ruth, Anthony; Bajpai, Anshumaan; Vietmeyer, Felix; Wang, Yuanxing; Brennan, Michael; Pang, Yunsong; Werellapatha, Kalpani; Bunker, Bruce; Chattopadhyay, Soma; Luo, Tengfei; Janko, Boldizsar; Fay, Patrick; Kuno, Masaru

2017-06-14

We report for the first time the synthesis of large, free-standing, Mo 2 O 2 (μ-S) 2 (Et 2 dtc) 2 (MoDTC) nanosheets (NSs), which exhibit an electron-beam induced crystalline-to-amorphous phase transition. Both electron beam ionization and femtosecond (fs) optical excitation induce the phase transition, which is size-, morphology-, and composition-preserving. Resulting NSs are the largest, free-standing regularly shaped two-dimensional amorphous nanostructures made to date. More importantly, amorphization is accompanied by dramatic changes to the NS electrical and optical response wherein resulting amorphous species exhibit room-temperature conductivities 5 orders of magnitude larger than those of their crystalline counterparts. This enhancement likely stems from the amorphization-induced formation of sulfur vacancy-related defects and is supported by temperature-dependent transport measurements, which reveal efficient variable range hopping. MoDTC NSs represent one instance of a broader class of transition metal carbamates likely having applications because of their intriguing electrical properties as well as demonstrated ability to toggle metal oxidation states.

Concrete Model Checking with Abstract Matching and Refinement

NASA Technical Reports Server (NTRS)

Pasareanu Corina S.; Peianek Radek; Visser, Willem

2005-01-01

We propose an abstraction-based model checking method which relies on refinement of an under-approximation of the feasible behaviors of the system under analysis. The method preserves errors to safety properties, since all analyzed behaviors are feasible by definition. The method does not require an abstract transition relation to he generated, but instead executes the concrete transitions while storing abstract versions of the concrete states, as specified by a set of abstraction predicates. For each explored transition. the method checks, with the help of a theorem prover, whether there is any loss of precision introduced by abstraction. The results of these checks are used to decide termination or to refine the abstraction, by generating new abstraction predicates. If the (possibly infinite) concrete system under analysis has a finite bisimulation quotient, then the method is guaranteed to eventually explore an equivalent finite bisimilar structure. We illustrate the application of the approach for checking concurrent programs. We also show how a lightweight variant can be used for efficient software testing.

Photocarrier generation from interlayer charge-transfer transitions in WS2-graphene heterostructures

PubMed Central

Yuan, Long; Chung, Ting-Fung; Kuc, Agnieszka; Wan, Yan; Xu, Yang; Chen, Yong P.; Heine, Thomas; Huang, Libai

2018-01-01

Efficient interfacial carrier generation in van der Waals heterostructures is critical for their electronic and optoelectronic applications. We demonstrate broadband photocarrier generation in WS2-graphene heterostructures by imaging interlayer coupling–dependent charge generation using ultrafast transient absorption microscopy. Interlayer charge-transfer (CT) transitions and hot carrier injection from graphene allow carrier generation by excitation as low as 0.8 eV below the WS2 bandgap. The experimentally determined interlayer CT transition energies are consistent with those predicted from the first-principles band structure calculation. CT interactions also lead to additional carrier generation in the visible spectral range in the heterostructures compared to that in the single-layer WS2 alone. The lifetime of the charge-separated states is measured to be ~1 ps. These results suggest that interlayer interactions make graphene–two-dimensional semiconductor heterostructures very attractive for photovoltaic and photodetector applications because of the combined benefits of high carrier mobility and enhanced broadband photocarrier generation. PMID:29423439

The Effect of SiC Polytypes on the Heat Distribution Efficiency of a Phase Change Memory.

NASA Astrophysics Data System (ADS)

Aziz, M. S.; Mohammed, Z.; Alip, R. I.

2018-03-01

The amorphous to crystalline transition of germanium-antimony-tellurium (GST) using three types of silicon carbide’s structure as a heating element was investigated. Simulation was done using COMSOL Multiphysic 5.0 software with separate heater structure. Silicon carbide (SiC) has three types of structure; 3C-SiC, 4H-SiC and 6H-SiC. These structures have a different thermal conductivity. The temperature of GST and phase transition of GST can be obtained from the simulation. The temperature of GST when using 3C-SiC, 4H-SiC and 6H-SiC are 467K, 466K and 460K, respectively. The phase transition of GST from amorphous to crystalline state for three type of SiC’s structure can be determined in this simulation. Based on the result, the thermal conductivity of SiC can affecting the temperature of GST and changed of phase change memory (PCM).

Extended Lagrangian Excited State Molecular Dynamics

DOE PAGES

Bjorgaard, Josiah August; Sheppard, Daniel Glen; Tretiak, Sergei; ...

2018-01-09

In this work, an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both formore » the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).« less

A multi-state trajectory method for non-adiabatic dynamics simulations

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

Tao, Guohua, E-mail: taogh@pkusz.edu.cn

2016-03-07

A multi-state trajectory approach is proposed to describe nuclear-electron coupled dynamics in nonadiabatic simulations. In this approach, each electronic state is associated with an individual trajectory, among which electronic transition occurs. The set of these individual trajectories constitutes a multi-state trajectory, and nuclear dynamics is described by one of these individual trajectories as the system is on the corresponding state. The total nuclear-electron coupled dynamics is obtained from the ensemble average of the multi-state trajectories. A variety of benchmark systems such as the spin-boson system have been tested and the results generated using the quasi-classical version of the method showmore » reasonably good agreement with the exact quantum calculations. Featured in a clear multi-state picture, high efficiency, and excellent numerical stability, the proposed method may have advantages in being implemented to realistic complex molecular systems, and it could be straightforwardly applied to general nonadiabatic dynamics involving multiple states.« less

Extended Lagrangian Excited State Molecular Dynamics

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

Bjorgaard, Josiah August; Sheppard, Daniel Glen; Tretiak, Sergei

In this work, an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both formore » the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).« less

Extended Lagrangian Excited State Molecular Dynamics.

PubMed

Bjorgaard, J A; Sheppard, D; Tretiak, S; Niklasson, A M N

2018-02-13

An extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born-Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a time-dependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both for the self-consistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. The XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree-Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).

Enabling online studies of conceptual relationships between medical terms: developing an efficient web platform.

PubMed

Albin, Aaron; Ji, Xiaonan; Borlawsky, Tara B; Ye, Zhan; Lin, Simon; Payne, Philip Ro; Huang, Kun; Xiang, Yang

2014-10-07

The Unified Medical Language System (UMLS) contains many important ontologies in which terms are connected by semantic relations. For many studies on the relationships between biomedical concepts, the use of transitively associated information from ontologies and the UMLS has been shown to be effective. Although there are a few tools and methods available for extracting transitive relationships from the UMLS, they usually have major restrictions on the length of transitive relations or on the number of data sources. Our goal was to design an efficient online platform that enables efficient studies on the conceptual relationships between any medical terms. To overcome the restrictions of available methods and to facilitate studies on the conceptual relationships between medical terms, we developed a Web platform, onGrid, that supports efficient transitive queries and conceptual relationship studies using the UMLS. This framework uses the latest technique in converting natural language queries into UMLS concepts, performs efficient transitive queries, and visualizes the result paths. It also dynamically builds a relationship matrix for two sets of input biomedical terms. We are thus able to perform effective studies on conceptual relationships between medical terms based on their relationship matrix. The advantage of onGrid is that it can be applied to study any two sets of biomedical concept relations and the relations within one set of biomedical concepts. We use onGrid to study the disease-disease relationships in the Online Mendelian Inheritance in Man (OMIM). By crossvalidating our results with an external database, the Comparative Toxicogenomics Database (CTD), we demonstrated that onGrid is effective for the study of conceptual relationships between medical terms. onGrid is an efficient tool for querying the UMLS for transitive relations, studying the relationship between medical terms, and generating hypotheses.

Atomic Processes for XUV Lasers: Alkali Atoms and Ions

NASA Astrophysics Data System (ADS)

Dimiduk, David Paul

The development of extreme ultraviolet (XUV) lasers is dependent upon knowledge of processes in highly excited atoms. Described here are spectroscopy experiments which have identified and characterized certain autoionizing energy levels in core-excited alkali atoms and ions. Such levels, termed quasi-metastable, have desirable characteristics as upper levels for efficient, powerful XUV lasers. Quasi -metastable levels are among the most intense emission lines in the XUV spectra of core-excited alkalis. Laser experiments utilizing these levels have proved to be useful in characterizing other core-excited levels. Three experiments to study quasi-metastable levels are reported. The first experiment is vacuum ultraviolet (VUV) absorption spectroscopy on the Cs 109 nm transitions using high-resolution laser techniques. This experiment confirms the identification of transitions to a quasi-metastable level, estimates transition oscillator strengths, and estimates the hyperfine splitting of the quasi-metastable level. The second experiment, XUV emission spectroscopy of Ca II and Sr II in a microwave-heated plasma, identifies transitions from quasi-metastable levels in these ions, and provides confirming evidence of their radiative, rather than autoionizing, character. In the third experiment, core-excited Ca II ions are produced by inner-shell photoionization of Ca with soft x-rays from a laser-produced plasma. This preliminary experiment demonstrated a method of creating large numbers of these highly-excited ions for future spectroscopic experiments. Experimental and theoretical evidence suggests the CA II 3{ rm p}^5 3d4s ^4 {rm F}^circ_{3/2 } quasi-metastable level may be directly pumped via a dipole ionization process from the Ca I ground state. The direct process is permitted by J conservation, and occurs due to configuration mixing in the final state and possibly the initial state as well. The experiments identifying and characterizing quasi-metastable levels are compared to calculations using the Hartree-Fock code RCN/RCG. Calculated parameters include energy levels, wavefunctions, and transition rates. Based on an extension of this code, earlier unexplained experiments showing strong two-electron radiative transitions from quasi-metastable levels are now understood.

Highly Efficient Gating of Electrically Actuated Nanochannels for Pulsatile Drug Delivery Stemming from a Reversible Wettability Switch.

PubMed

Zhang, Qianqian; Kang, Jianxin; Xie, Zhiqiang; Diao, Xungang; Liu, Zhaoyue; Zhai, Jin

2018-01-01

Many ion channels in the cell membrane are believed to function as gates that control the water and ion flow through the transitions between an inherent hydrophobic state and a stimuli-induced hydration state. The construction of nanofluidic gating systems with high gating efficiency and reversibility is inspired by this hydrophobic gating behavior. A kind of electrically actuated nanochannel is developed by integrating a polypyrrole (PPy) micro/nanoporous film doped with perfluorooctanesulfonate ions onto an anodic aluminum oxide nanoporous membrane. Stemming from the reversible wettability switch of the doped PPy film in response to the applied redox potentials, the nanochannels exhibit highly efficient and reversible gating behaviors. The optimized gating ratio is over 10 5 , which is an ultrahigh value when compared with that of the existing reversibly gated nanochannels with comparable pore diameters. Furthermore, the gating behavior of the electrically actuated nanochannels shows excellent repeatability and stability. Based on this highly efficient and reversible gating function, the electrically actuated nanochannels are further applied for drug delivery, which achieves the pulsatile release of two water-soluble drug models. The electrically actuated nanochannels may find potential applications in accurate and on-demand drug therapy. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic Two-Transition-Induced Enhancement of Emission Efficiency in Polymer Light-Emitting Diodes

PubMed Central

Chen, Ren-Ai; Wang, Cong; Li, Sheng; George, Thomas F.

2013-01-01

With the development of experimental techniques, effective injection and transportation of electrons is proven as a way to obtain polymer light-emitting diodes (PLEDs) with high quantum efficiency. This paper reveals a valid mechanism for the enhancement of quantum efficiency in PLEDs. When an external electric field is applied, the interaction between a negative polaron and triplet exciton leads to an electronic two-transition process, which induces the exciton to emit light and thus improve the emission efficiency of PLEDs. PMID:28809346

Efficient time-dependent density functional theory approximations for hybrid density functionals: analytical gradients and parallelization.

PubMed

Petrenko, Taras; Kossmann, Simone; Neese, Frank

2011-02-07

In this paper, we present the implementation of efficient approximations to time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation (TDA) for hybrid density functionals. For the calculation of the TDDFT/TDA excitation energies and analytical gradients, we combine the resolution of identity (RI-J) algorithm for the computation of the Coulomb terms and the recently introduced "chain of spheres exchange" (COSX) algorithm for the calculation of the exchange terms. It is shown that for extended basis sets, the RIJCOSX approximation leads to speedups of up to 2 orders of magnitude compared to traditional methods, as demonstrated for hydrocarbon chains. The accuracy of the adiabatic transition energies, excited state structures, and vibrational frequencies is assessed on a set of 27 excited states for 25 molecules with the configuration interaction singles and hybrid TDDFT/TDA methods using various basis sets. Compared to the canonical values, the typical error in transition energies is of the order of 0.01 eV. Similar to the ground-state results, excited state equilibrium geometries differ by less than 0.3 pm in the bond distances and 0.5° in the bond angles from the canonical values. The typical error in the calculated excited state normal coordinate displacements is of the order of 0.01, and relative error in the calculated excited state vibrational frequencies is less than 1%. The errors introduced by the RIJCOSX approximation are, thus, insignificant compared to the errors related to the approximate nature of the TDDFT methods and basis set truncation. For TDDFT/TDA energy and gradient calculations on Ag-TB2-helicate (156 atoms, 2732 basis functions), it is demonstrated that the COSX algorithm parallelizes almost perfectly (speedup ~26-29 for 30 processors). The exchange-correlation terms also parallelize well (speedup ~27-29 for 30 processors). The solution of the Z-vector equations shows a speedup of ~24 on 30 processors. The parallelization efficiency for the Coulomb terms can be somewhat smaller (speedup ~15-25 for 30 processors), but their contribution to the total calculation time is small. Thus, the parallel program completes a Becke3-Lee-Yang-Parr energy and gradient calculation on the Ag-TB2-helicate in less than 4 h on 30 processors. We also present the necessary extension of the Lagrangian formalism, which enables the calculation of the TDDFT excited state properties in the frozen-core approximation. The algorithms described in this work are implemented into the ORCA electronic structure system.

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.

Search for a massive short-lived axion in nuclear transitions

NASA Astrophysics Data System (ADS)

Hatzikoutelis, Athanasios

Recent reports of the possible existence of an Axion with mass = 9.5 MeV and lifetime less than 10-14 sec do not contradict any negative results of the 20-year long search. The present work aims at confirming or disproving these reports. An Axion may compete with M1 nuclear transitions and decay into a e+-e- pair, producing events with high angle separation, thus being detectable in the presence of internal pair conversion which favors small separation angles. In the present experiment the M1 transitions from two discrete states in 12C were produced using a (d,n) reaction. A hermetic array of plastic scintillator detectors for e+-e- pairs from nuclear transitions was upgraded to 65 elements covering 50% of 4pi. A target chamber made of carbon fiber/epoxy resin, with wall thickness 0.8 mm, was introduced which absorbs only 172. 2 keV of the kinetic energy of minimum ionizing e+/e-. A neutron detector with total efficiency of 3% was constructed to measure the time of flight of neutrons. The detectors and chamber were installed on the beam line of the Stony Brook heavy ion LINAC. A test run was conducted using the reaction 11B(p,e+e-)12C (Ep = 7.2 MeV) to populate the Giant Dipole Resonance of 12C. The observation of the IPC from the 22.6-MeV E1 transition to the ground state of 12C established the pair-energy line-shape and produced an absolute pairenergy calibration. The angular correlation distribution of the pairs was found to be in agreement with the Born and point nucleus approximation of E1 angular correlations. A data run with the stripping reaction 11B(d,n)12C* (Ed = 7.2 MeV) populated the (Ipi,T) = (1+,1) 15.11-MeV and the (1 +,0) 12.7-MeV states of 12C. Detected pair events without neutron coincidence required showed a clear and strong peak of the 15.11 MeV to ground state transition. Analysis of these data agreed with angular correlations of M1 internal pair conversion. These did not support the earlier work and showed no evidence of an Axion emitted in the transition. A second test with neutron coincidence required, demonstrated that the full experiment is working as designed. However, for the kinematically complete experiment including neutron coincidence the rate of good events was found to be only 4--6 events/hr. A statistically decisive test will take data runs of about six months.

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.

Slow induction of photosynthesis on shade to sun transitions in wheat may cost at least 21% of productivity.

PubMed

Taylor, Samuel H; Long, Stephen P

2017-09-26

Wheat is the second most important direct source of food calories in the world. After considerable improvement during the Green Revolution, increase in genetic yield potential appears to have stalled. Improvement of photosynthetic efficiency now appears a major opportunity in addressing the sustainable yield increases needed to meet future food demand. Effort, however, has focused on increasing efficiency under steady-state conditions. In the field, the light environment at the level of individual leaves is constantly changing. The speed of adjustment of photosynthetic efficiency can have a profound effect on crop carbon gain and yield. Flag leaves of wheat are the major photosynthetic organs supplying the grain of wheat, and will be intermittently shaded throughout a typical day. Here, the speed of adjustment to a shade to sun transition in these leaves was analysed. On transfer to sun conditions, the leaf required about 15 min to regain maximum photosynthetic efficiency. In vivo analysis based on the responses of leaf CO 2 assimilation ( A ) to intercellular CO 2 concentration ( c i ) implied that the major limitation throughout this induction was activation of the primary carboxylase of C3 photosynthesis, ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco). This was followed in importance by stomata, which accounted for about 20% of the limitation. Except during the first few seconds, photosynthetic electron transport and regeneration of the CO 2 acceptor molecule, ribulose-1,5-bisphosphate (RubP), did not affect the speed of induction. The measured kinetics of Rubisco activation in the sun and de-activation in the shade were predicted from the measurements. These were combined with a canopy ray tracing model that predicted intermittent shading of flag leaves over the course of a June day. This indicated that the slow adjustment in shade to sun transitions could cost 21% of potential assimilation.This article is part of the themed issue 'Enhancing photosynthesis in crop plants: targets for improvement'. © 2017 The Authors.

DFT/TD-semiempirical study on the structural and electronic properties and absorption spectra of supramolecular fullerene-porphyrine-metalloporphyrine triads based dye-sensitized solar cells.

PubMed

Rezvani, M; Darvish Ganji, M; Jameh-Bozorghi, S; Niazi, A

2018-04-05

In the present work density functional theory (DFT) and time-dependent semiempirical ZNIDO/S (TD-ZNIDO/S) methods have been used to investigate the ground state geometries, electronic structures and excited state properties of triad systems. The influences of the type of metal in the porphyrin ring, change in bridge position and porphyrine-ZnP duplicate on the energies of frontier molecular orbital and UV-Vis spectra has been studied. Geometry optimization, the energy levels and electron density of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), chemical hardness (η), electrophilicity index (ω), electron accepting power (ω + ) were calculated using ZINDO/S method to predict which molecule is the most efficient with a great capability to be used as a triad molecule in solar industry. Moreover the light harvesting efficiency (LHE) was calculated by means of the oscillator strengths which are obtained by TD-ZINDO/S calculation. Theoretical studies of the electronic spectra by ZINDO/S method were helpful in interpreting the observed electronic transitions. This aspect was systematically explored in a series of C 60 -Porphyrine-Metalloporphyrine (C 60 -P-Mp) triad system with M being Fe, Co, Ni, Ti, and Zn. Generally, transition metal coordination compounds are used as effective sensitizers, due to their intense charge-transfer absorption over the whole visible range and highly efficient metal-to-ligand charge transfer. We aim to optimize the performance of the title solar cells by altering the frontier orbital energy gaps. The results reveal that cell efficiency can be enhanced by metal functionalization of the free base porphyrin. Ti-porphyrin was found to be the most efficient dye sensitizer for dye sensitized solar cells (DSSCs) based on C 60 -P-Mptriad system due to C 60 -Por-TiP complex has lower chemical hardness, gap energy and chemical potential as well as higher electron accepting power among other complexes. In addition, the performance of solar cells favors better with doubly and increasing the π conjugated of the bridge. Copyright © 2018 Elsevier B.V. All rights reserved.

DFT/TD-semiempirical study on the structural and electronic properties and absorption spectra of supramolecular fullerene-porphyrine-metalloporphyrine triads based dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Rezvani, M.; Darvish Ganji, M.; Jameh-Bozorghi, S.; Niazi, A.

2018-04-01

In the present work density functional theory (DFT) and time-dependent semiempirical ZNIDO/S (TD-ZNIDO/S) methods have been used to investigate the ground state geometries, electronic structures and excited state properties of triad systems. The influences of the type of metal in the porphyrin ring, change in bridge position and porphyrine-ZnP duplicate on the energies of frontier molecular orbital and UV-Vis spectra has been studied. Geometry optimization, the energy levels and electron density of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), chemical hardness (η), electrophilicity index (ω), electron accepting power (ω+) were calculated using ZINDO/S method to predict which molecule is the most efficient with a great capability to be used as a triad molecule in solar industry. Moreover the light harvesting efficiency (LHE) was calculated by means of the oscillator strengths which are obtained by TD-ZINDO/S calculation. Theoretical studies of the electronic spectra by ZINDO/S method were helpful in interpreting the observed electronic transitions. This aspect was systematically explored in a series of C60-Porphyrine-Metalloporphyrine (C60-P-Mp) triad system with M being Fe, Co, Ni, Ti, and Zn. Generally, transition metal coordination compounds are used as effective sensitizers, due to their intense charge-transfer absorption over the whole visible range and highly efficient metal-to-ligand charge transfer. We aim to optimize the performance of the title solar cells by altering the frontier orbital energy gaps. The results reveal that cell efficiency can be enhanced by metal functionalization of the free base porphyrin. Ti-porphyrin was found to be the most efficient dye sensitizer for dye sensitized solar cells (DSSCs) based on C60-P-Mptriad system due to C60-Por-TiP complex has lower chemical hardness, gap energy and chemical potential as well as higher electron accepting power among other complexes. In addition, the performance of solar cells favors better with doubly and increasing the π conjugated of the bridge.

A Pipelined Non-Deterministic Finite Automaton-Based String Matching Scheme Using Merged State Transitions in an FPGA

PubMed Central

Choi, Kang-Il

2016-01-01

This paper proposes a pipelined non-deterministic finite automaton (NFA)-based string matching scheme using field programmable gate array (FPGA) implementation. The characteristics of the NFA such as shared common prefixes and no failure transitions are considered in the proposed scheme. In the implementation of the automaton-based string matching using an FPGA, each state transition is implemented with a look-up table (LUT) for the combinational logic circuit between registers. In addition, multiple state transitions between stages can be performed in a pipelined fashion. In this paper, it is proposed that multiple one-to-one state transitions, called merged state transitions, can be performed with an LUT. By cutting down the number of used LUTs for implementing state transitions, the hardware overhead of combinational logic circuits is greatly reduced in the proposed pipelined NFA-based string matching scheme. PMID:27695114

A Pipelined Non-Deterministic Finite Automaton-Based String Matching Scheme Using Merged State Transitions in an FPGA.

PubMed

Kim, HyunJin; Choi, Kang-Il

2016-01-01

This paper proposes a pipelined non-deterministic finite automaton (NFA)-based string matching scheme using field programmable gate array (FPGA) implementation. The characteristics of the NFA such as shared common prefixes and no failure transitions are considered in the proposed scheme. In the implementation of the automaton-based string matching using an FPGA, each state transition is implemented with a look-up table (LUT) for the combinational logic circuit between registers. In addition, multiple state transitions between stages can be performed in a pipelined fashion. In this paper, it is proposed that multiple one-to-one state transitions, called merged state transitions, can be performed with an LUT. By cutting down the number of used LUTs for implementing state transitions, the hardware overhead of combinational logic circuits is greatly reduced in the proposed pipelined NFA-based string matching scheme.

Improving Upon String Methods for Transition State Discovery.

PubMed

Chaffey-Millar, Hugh; Nikodem, Astrid; Matveev, Alexei V; Krüger, Sven; Rösch, Notker

2012-02-14

Transition state discovery via application of string methods has been researched on two fronts. The first front involves development of a new string method, named the Searching String method, while the second one aims at estimating transition states from a discretized reaction path. The Searching String method has been benchmarked against a number of previously existing string methods and the Nudged Elastic Band method. The developed methods have led to a reduction in the number of gradient calls required to optimize a transition state, as compared to existing methods. The Searching String method reported here places new beads on a reaction pathway at the midpoint between existing beads, such that the resolution of the path discretization in the region containing the transition state grows exponentially with the number of beads. This approach leads to favorable convergence behavior and generates more accurate estimates of transition states from which convergence to the final transition states occurs more readily. Several techniques for generating improved estimates of transition states from a converged string or nudged elastic band have been developed and benchmarked on 13 chemical test cases. Optimization approaches for string methods, and pitfalls therein, are discussed.

Policy evaluation for a bus-based transit system: the case study of Busan, Korea

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

Lew, K.S.

This study considers a quite specific set of dimensions of transit evaluation as a comprehensive management-strategy approach for addressing the ongoing problems of urban public transit systems and apply them in a case study. With increasing difficulties in providing effective public transportation, attention in this study was placed on providing for the movement of people in an efficient and equitable manner. This study was therefore concerned with just identifying and evaluating policy options that are feasible within the socio-economic and political context of the Busan metropolitan area and, in particular, how the criteria of efficiency and equity can best bemore » achieved by implementing transit policy alternatives. In the absence of long-run major public investment in urban transportation, the criteria of both efficiency and equity can only be furthered through managerial strategies applied within a systematic evaluative framework. By emphasizing the planning, operational, and managerial considerations of fixed-route bus transit in Busan, it has been acknowledged that efficient and equitable public transportation can be provided through a variety of social, economic, political, and institutional arrangements that are possible to apply from a policy viewpoint in the immediate future.« less

Estimation of optimum density and temperature for maximum efficiency of tin ions in Z discharge extreme ultraviolet sources

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

Masnavi, Majid; Nakajima, Mitsuo; Hotta, Eiki

Extreme ultraviolet (EUV) discharge-based lamps for EUV lithography need to generate extremely high power in the narrow spectrum band of 13.5{+-}0.135 nm. A simplified collisional-radiative model and radiative transfer solution for an isotropic medium were utilized to investigate the wavelength-integrated light outputs in tin (Sn) plasma. Detailed calculations using the Hebrew University-Lawrence Livermore atomic code were employed for determination of necessary atomic data of the Sn{sup 4+} to Sn{sup 13+} charge states. The result of model is compared with experimental spectra from a Sn-based discharge-produced plasma. The analysis reveals that considerably larger efficiency compared to the so-called efficiency of amore » black-body radiator is formed for the electron density {approx_equal}10{sup 18} cm{sup -3}. For higher electron density, the spectral efficiency of Sn plasma reduces due to the saturation of resonance transitions.« less

HRSSA – Efficient hybrid stochastic simulation for spatially homogeneous biochemical reaction networks

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

Marchetti, Luca, E-mail: marchetti@cosbi.eu; Priami, Corrado, E-mail: priami@cosbi.eu; University of Trento, Department of Mathematics

This paper introduces HRSSA (Hybrid Rejection-based Stochastic Simulation Algorithm), a new efficient hybrid stochastic simulation algorithm for spatially homogeneous biochemical reaction networks. HRSSA is built on top of RSSA, an exact stochastic simulation algorithm which relies on propensity bounds to select next reaction firings and to reduce the average number of reaction propensity updates needed during the simulation. HRSSA exploits the computational advantage of propensity bounds to manage time-varying transition propensities and to apply dynamic partitioning of reactions, which constitute the two most significant bottlenecks of hybrid simulation. A comprehensive set of simulation benchmarks is provided for evaluating performance andmore » accuracy of HRSSA against other state of the art algorithms.« less

Nonadiabatic quantum dynamics and laser control of Br2 in solid argon.

PubMed

Accardi, A; Borowski, A; Kühn, O

2009-07-02

A five-dimensional reaction surface-vibronic coupling model is introduced to describe the B- to C-state predissociation dynamics of Br(2) occupying a double substitutional lattice site in a face-centered cubic argon crystal at low temperatures. The quantum dynamics driven by a Franck-Condon vertical excitation is investigated, revealing the role of matrix cage compression for efficient nonadiabatic transitions. Vibrational preexcitation of the Br(2) bond in the electronic ground state can be used to access a different regime of predissociation which does not require substantial matrix compression because the Franck-Condon window shifts into the energetic range of the B-C level crossing. Using optimal control theory, it is shown how vibrational preexcitation can be achieved via a pump-dump-type mechanism involving the repulsive C state.

A high efficient nanostructured filter based on functionalized carbon nanotube to reduce the tobacco-specific nitrosamines, NNK

NASA Astrophysics Data System (ADS)

Yoosefian, Mehdi

2018-03-01

Filtration efficiency of Pd and Ni loaded single-walled carbon nanotubes via the applicability of the adsorption process for the removal NNK, the tobacco-specific nitrosamines, from tobacco smoke were investigated using first-principles calculations. The thermal and mechanical stability of designed nanostructured filter could allow them to compete with typical commercially used. It is expected that the removal efficiency of the proposed nanostructured filter could also provide a promising adsorbent candidate in removing the environmental pollutant. The suggested separation mechanism in this study was discussed with frontier molecular orbital theory, natural bond orbital (NBO) analyses and the density of states in the density functional theory framework. Finally, by the Bader theory of atoms in molecules (AIM), the topological properties of the electron density contributions for intermolecular and intramolecular interactions has been analyzed. Calculations show that the transition metal-loaded SWCNT exhibit strong affinity toward the NNK molecules.

Cold-air performance of a 15.41-cm-tip-diameter axial-flow power turbine with variable-area stator designed for a 75-kW automotive gas turbine engine

NASA Technical Reports Server (NTRS)

Mclallin, K. L.; Kofskey, M. G.; Wong, R. Y.

1982-01-01

An experimental evaluation of the aerodynamic performance of the axial flow, variable area stator power turbine stage for the Department of Energy upgraded automotive gas turbine engine was conducted in cold air. The interstage transition duct, the variable area stator, the rotor, and the exit diffuser were included in the evaluation of the turbine stage. The measured total blading efficiency was 0.096 less than the design value of 0.85. Large radial gradients in flow conditions were found at the exit of the interstage duct that adversely affected power turbine performance. Although power turbine efficiency was less than design, the turbine operating line corresponding to the steady state road load power curve was within 0.02 of the maximum available stage efficiency at any given speed.

Structure Dependence of Lysosomal Transit of Chitosan-Based Polyplexes for Gene Delivery.

PubMed

Thibault, Marc; Lavertu, Marc; Astolfi, Mélina; Buschmann, Michael D

2016-10-01

Chitosan-based polyplexes are known to traffic through lysosomes for a relatively long time, independent of the degree of deacetylation (DDA) and the number average molecular weight (Mn) of the polymer, even though both of these parameters have profound effects on polyplex stability and transfection efficiency. A better understanding of the lysosomal barrier is paramount to the rational design of vectors capable of overcoming obstacles to transgene expression. The aim of the present study was to investigate if lysosomal transit affects chitosan-based polyplex transfection efficiency in a structure-dependent (DDA, Mn) manner. Toward this end, we analyzed the effects of intracellular trafficking modifying agents on transfection efficiency and intracellular vesicular trafficking of polyplexes with different structural properties and stabilities or nucleic acid binding affinity. The use of agents that modify endosome/lysosome acidification and transit processes by distinct mechanisms and their effect on cell viability, polyplex uptake, vesicular trafficking, and transfection efficiency revealed novel and strong chitosan structure-dependent consequences of lysosomal transit. Inhibiting lysosomal transit using chloroquine significantly increased the efficiency of unstable polyplexes, while having minimal effects for polyplexes with intermediate or high stability. In parallel, specifically inhibiting the acidification of vesicles abrogated transfection for all formulations, suggesting that vesicular acidification is essential to promote transfection, most probably by facilitating lysosomal escape. These results provide novel insights into the structure-performance relationship of chitosan-based gene delivery systems.

Lasing characteristics of gas mixtures involving UFG: Application to nuclear pumping of lasers

NASA Technical Reports Server (NTRS)

Verdeyen, J. T.; Eden, J. G.

1980-01-01

Intense blue-green fluorescence from a structured band centered at lambda approximately 484 nm was observed from Ar, CF3I and NF3 gas mixtures excited by an electron beam. This emission was tentatively assigned to the E yields A transition of the iodine monofluoride (IF) molecule. The fluorescence efficiency of the IF(E yields A) band and the IF (E) state radiative lifetime were estimated to be approximately 6% and 15 ns, respectively. The emission band structure, the short IF(E) radiative lifetime and the Franck-Condon shift between the E and A states suggest that IF is an attractive candidate for a blue-green laser.

Improved techniques for outgoing wave variational principle calculations of converged state-to-state transition probabilities for chemical reactions

NASA Technical Reports Server (NTRS)

Mielke, Steven L.; Truhlar, Donald G.; Schwenke, David W.

1991-01-01

Improved techniques and well-optimized basis sets are presented for application of the outgoing wave variational principle to calculate converged quantum mechanical reaction probabilities. They are illustrated with calculations for the reactions D + H2 yields HD + H with total angular momentum J = 3 and F + H2 yields HF + H with J = 0 and 3. The optimization involves the choice of distortion potential, the grid for calculating half-integrated Green's functions, the placement, width, and number of primitive distributed Gaussians, and the computationally most efficient partition between dynamically adapted and primitive basis functions. Benchmark calculations with 224-1064 channels are presented.

Effect of ion pairing on the fluorescence of berberine, a natural isoquinoline alkaloid

NASA Astrophysics Data System (ADS)

Megyesi, Mónika; Biczók, László

2007-10-01

Effect of association with chloride or perchlorate anions on the fluorescence properties of berberine, a cationic isoquinoline alkaloid, has been studied. Interaction with Cl - caused more efficient fluorescence quenching; it significantly accelerated the radiationless deactivation and slowed down the radiative transition. Combined analysis of spectrophotometric, steady-state and time-resolved fluorescence results provided 1.5 × 10 5 M -1 for the equilibrium constant of ion pairing with Cl - in CH 2Cl 2. Both ion pairing and enrichment of the microenvironment of berberine in ions led to excited state quenching in solvents of medium polarity, but only the latter effect was observed in the presence of perchlorates in butyronitrile.

Applications of connected vehicle infrastructure technologies to enhance transit service efficiency and safety.

DOT National Transportation Integrated Search

2016-09-30

Many transit agencies provide real-time operational information and trip-planning tools through phone, Web, and smartphone applications. These services utilize a one-way information flow from transit agencies to transit users. Current smartphone tech...

Best practices in transit service planning : final report, March 2009.

DOT National Transportation Integrated Search

2009-03-01

The provision of cost efficient and effective bus transit service is the basic premise upon which transit service is developed and the goal that all public transportations agencies strive to achieve. To attain this goal, public transit agencies must ...

Energy conversion of X-ray, ultraviolet and infrared radiation in Gd2O3 crystals doped with Er3+ ions

NASA Astrophysics Data System (ADS)

Trofimova, E. S.; Pustovarov, V. A.; Kuznetsova, Yu. A.; Zatsepin, A. F.

2017-09-01

Spectra of photoluminescence (PL) and X-ray excited luminescence (XRL) in region of 1.5-5.0 eV, PL excitation spectra (2.8-5.8 eV), PL decay kinetics were measured in Gd2O3 crystals doped both with Er3+ and Zn2+ ions. Synchrotron radiation (VEPP-3 storage ring, Novosibirsk, Russia) were used for XRL measurements. PL spectra were studied at room temperature and T= 88 K under excitation with energy Eexc: a) in fundamental absorption region (Eexc≥Eg); b) in intracenter excitation region (Eexc

Putting Humpty-Dumpty Together: Clustering the Functional Dynamics of Single Biomolecular Machines Such as the Spliceosome.

PubMed

Rohlman, C E; Blanco, M R; Walter, N G

2016-01-01

The spliceosome is a biomolecular machine that, in all eukaryotes, accomplishes site-specific splicing of introns from precursor messenger RNAs (pre-mRNAs) with high fidelity. Operating at the nanometer scale, where inertia and friction have lost the dominant role they play in the macroscopic realm, the spliceosome is highly dynamic and assembles its active site around each pre-mRNA anew. To understand the structural dynamics underlying the molecular motors, clocks, and ratchets that achieve functional accuracy in the yeast spliceosome (a long-standing model system), we have developed single-molecule fluorescence resonance energy transfer (smFRET) approaches that report changes in intra- and intermolecular interactions in real time. Building on our work using hidden Markov models (HMMs) to extract kinetic and conformational state information from smFRET time trajectories, we recognized that HMM analysis of individual state transitions as independent stochastic events is insufficient for a biomolecular machine as complex as the spliceosome. In this chapter, we elaborate on the recently developed smFRET-based Single-Molecule Cluster Analysis (SiMCAn) that dissects the intricate conformational dynamics of a pre-mRNA through the splicing cycle in a model-free fashion. By leveraging hierarchical clustering techniques developed for Bioinformatics, SiMCAn efficiently analyzes large datasets to first identify common molecular behaviors. Through a second level of clustering based on the abundance of dynamic behaviors exhibited by defined functional intermediates that have been stalled by biochemical or genetic tools, SiMCAn then efficiently assigns pre-mRNA FRET states and transitions to specific splicing complexes, with the potential to find heretofore undescribed conformations. SiMCAn thus arises as a general tool to analyze dynamic cellular machines more broadly. © 2016 Elsevier Inc. All rights reserved.

Analyzing milestoning networks for molecular kinetics: definitions, algorithms, and examples.

PubMed

Viswanath, Shruthi; Kreuzer, Steven M; Cardenas, Alfredo E; Elber, Ron

2013-11-07

Network representations are becoming increasingly popular for analyzing kinetic data from techniques like Milestoning, Markov State Models, and Transition Path Theory. Mapping continuous phase space trajectories into a relatively small number of discrete states helps in visualization of the data and in dissecting complex dynamics to concrete mechanisms. However, not only are molecular networks derived from molecular dynamics simulations growing in number, they are also getting increasingly complex, owing partly to the growth in computer power that allows us to generate longer and better converged trajectories. The increased complexity of the networks makes simple interpretation and qualitative insight of the molecular systems more difficult to achieve. In this paper, we focus on various network representations of kinetic data and algorithms to identify important edges and pathways in these networks. The kinetic data can be local and partial (such as the value of rate coefficients between states) or an exact solution to kinetic equations for the entire system (such as the stationary flux between vertices). In particular, we focus on the Milestoning method that provides fluxes as the main output. We proposed Global Maximum Weight Pathways as a useful tool for analyzing molecular mechanism in Milestoning networks. A closely related definition was made in the context of Transition Path Theory. We consider three algorithms to find Global Maximum Weight Pathways: Recursive Dijkstra's, Edge-Elimination, and Edge-List Bisection. The asymptotic efficiency of the algorithms is analyzed and numerical tests on finite networks show that Edge-List Bisection and Recursive Dijkstra's algorithms are most efficient for sparse and dense networks, respectively. Pathways are illustrated for two examples: helix unfolding and membrane permeation. Finally, we illustrate that networks based on local kinetic information can lead to incorrect interpretation of molecular mechanisms.

Molecular simulation of aqueous electrolyte solubility. 2. Osmotic ensemble Monte Carlo methodology for free energy and solubility calculations and application to NaCl.

PubMed

Moučka, Filip; Lísal, Martin; Škvor, Jiří; Jirsák, Jan; Nezbeda, Ivo; Smith, William R

2011-06-23

We present a new and computationally efficient methodology using osmotic ensemble Monte Carlo (OEMC) simulation to calculate chemical potential-concentration curves and the solubility of aqueous electrolytes. The method avoids calculations for the solid phase, incorporating readily available data from thermochemical tables that are based on well-defined reference states. It performs simulations of the aqueous solution at a fixed number of water molecules, pressure, temperature, and specified overall electrolyte chemical potential. Insertion/deletion of ions to/from the system is implemented using fractional ions, which are coupled to the system via a coupling parameter λ that varies between 0 (no interaction between the fractional ions and the other particles in the system) and 1 (full interaction between the fractional ions and the other particles of the system). Transitions between λ-states are accepted with a probability following from the osmotic ensemble partition function. Biasing weights associated with the λ-states are used in order to efficiently realize transitions between them; these are determined by means of the Wang-Landau method. We also propose a novel scaling procedure for λ, which can be used for both nonpolarizable and polarizable models of aqueous electrolyte systems. The approach is readily extended to involve other solvents, multiple electrolytes, and species complexation reactions. The method is illustrated for NaCl, using SPC/E water and several force field models for NaCl from the literature, and the results are compared with experiment at ambient conditions. Good agreement is obtained for the chemical potential-concentration curve and the solubility prediction is reasonable. Future improvements to the predictions will require improved force field models.

Evaluation of the influence of ionization states and spacers in the thermotropic phase behaviour of amino acid-based cationic lipids and the transfection efficiency of their assemblies.

PubMed

Sarker, Satya Ranjan; Arai, Satoshi; Murate, Motohide; Takahashi, Hiroshi; Takata, Masaki; Kobayashi, Toshihide; Takeoka, Shinji

2012-01-17

The influence of both the ionization states and the hydrocarbon chain spacer of a series of amino acid-based cationic lipids was evaluated in terms of gene delivery efficiency and cytotoxicity to the COS-7 cell line and compared with that of Lipofectamine 2000. We synthesized a series of amino acid-based cationic lipids with different ionization states (i.e., -NH(2), -NH(3)(+)Cl(-) or -NH(3)(+)TFA(-)) in the lysine head group and different hydrocarbon chain spacers (i.e., 0, 3, 5 or 7 carbon atoms) between the hydrophilic head group and hydrophobic moieties. In the 3-carbon series, the cationic assemblies formed a micellar structure in the presence of -NH(3)(+)Cl(-) and a vesicular structure both in the presence of -NH(2) and -NH(3)(+)TFA(-). Differential scanning calorimetry (DSC) data revealed a significantly lower (8.1°C) gel-to-liquid crystalline phase transition temperature for cationic assemblies bearing -NH(3)(+)TFA(-) when compared to their -NH(2) counterparts. Furthermore, the zeta potential of cationic assemblies having -NH(3)(+)TFA(-) in the hydrophilic head group was maximum followed by -NH(3)(+)Cl(-) and -NH(2) irrespective of their hydrocarbon chain spacer length. The gene delivery efficiency in relation to the ionization states of the hydrophilic head group was as follows: -NH(3)(+)TFA(-)>-NH(3)(+)Cl(-)>-NH(2). Copyright © 2011 Elsevier B.V. All rights reserved.

Photoconductive gain and quantum efficiency of remotely doped Ge/Si quantum dot photodetectors

NASA Astrophysics Data System (ADS)

Yakimov, A. I.; Kirienko, V. V.; Armbrister, V. A.; Bloshkin, A. A.; Dvurechenskii, A. V.; Shklyaev, A. A.

2016-10-01

We study the effect of quantum dot charging on the mid-infrared photocurrent, optical gain, hole capture probability, and absorption quantum efficiency in remotely delta-doped Ge/Si quantum dot photodetectors. The dot occupation with holes is controlled by varying dot and doping densities. From our investigations of samples doped to contain from about one to nine holes per dot we observe an over 10 times gain enhancement and similar suppression of the hole capture probability with increased carrier population. The data are explained by quenching the capture process and increasing the photoexcited hole lifetime due to formation of the repulsive Coulomb potential of the extra holes inside the quantum dots. The normal incidence quantum efficiency is found to be strongly asymmetric with respect to applied bias polarity. Based on the polarization-dependent absorption measurements it is concluded that, at a positive voltage, when holes move toward the nearest δ-doping plane, photocurrent is originated from the bound-to-continuum transitions of holes between the ground state confined in Ge dots and the extended states of the Si matrix. At a negative bias polarity, the photoresponse is caused by optical excitation to a quasibound state confined near the valence band edge with subsequent tunneling to the Si valence band. In a latter case, the possibility of hole transfer into continuum states arises from the electric field generated by charge distributed between quantum dots and delta-doping planes.

Optimal quantum operations at zero energy cost

NASA Astrophysics Data System (ADS)

Chiribella, Giulio; Yang, Yuxiang

2017-08-01

Quantum technologies are developing powerful tools to generate and manipulate coherent superpositions of different energy levels. Envisaging a new generation of energy-efficient quantum devices, here we explore how coherence can be manipulated without exchanging energy with the surrounding environment. We start from the task of converting a coherent superposition of energy eigenstates into another. We identify the optimal energy-preserving operations, both in the deterministic and in the probabilistic scenario. We then design a recursive protocol, wherein a branching sequence of energy-preserving filters increases the probability of success while reaching maximum fidelity at each iteration. Building on the recursive protocol, we construct efficient approximations of the optimal fidelity-probability trade-off, by taking coherent superpositions of the different branches generated by probabilistic filtering. The benefits of this construction are illustrated in applications to quantum metrology, quantum cloning, coherent state amplification, and ancilla-driven computation. Finally, we extend our results to transitions where the input state is generally mixed and we apply our findings to the task of purifying quantum coherence.

High-performance organic light-emitting diodes comprising ultrastable glass layers

PubMed Central

Rodríguez-Viejo, Javier

2018-01-01

Organic light-emitting diodes (OLEDs) are one of the key solid-state light sources for various applications including small and large displays, automotive lighting, solid-state lighting, and signage. For any given commercial application, OLEDs need to perform at their best, which is judged by their device efficiency and operational stability. We present OLEDs that comprise functional layers fabricated as ultrastable glasses, which represent the thermodynamically most favorable and, thus, stable molecular conformation achievable nowadays in disordered solids. For both external quantum efficiencies and LT70 lifetimes, OLEDs with four different phosphorescent emitters show >15% enhancements over their respective reference devices. The only difference to the latter is the growth condition used for ultrastable glass layers that is optimal at about 85% of the materials’ glass transition temperature. These improvements are achieved through neither material refinements nor device architecture optimization, suggesting a general applicability of this concept to maximize the OLED performance, no matter which specific materials are used. PMID:29806029

Aza-Bambusurils En Route to Anion Transporters.

PubMed

Singh, Mandeep; Solel, Ephrath; Keinan, Ehud; Reany, Ofer

2016-06-20

Previous calculations of anion binding with various bambusuril analogs predicted that the replacement of oxygen by nitrogen atoms to produce semiaza-bambus[6]urils would award these new cavitands with multiple anion binding properties. This study validates the hypothesis by efficient synthesis, crystallography, thermogravimetric analysis and calorimetry. These unique host molecules are easily accessible from the corresponding semithio-bambusurils in a one-pot reaction, which converts a single anion receptor into a potential anion channel. Solid-state structures exhibit simultaneous accommodation of three anions, linearly positioned within the cavity along the main symmetry axis. The ability to hold anions at a short distance of about 4 Å is reminiscent of natural chloride channels in E. coli, which exhibit similar distances between their adjacent anion binding sites. The calculated transition-state energy for double-anion movement through the channel suggests that although these host-guest complexes are thermodynamically stable they enjoy high kinetic flexibility to render them efficient anion channels. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First Results on High-spin States in ^179Au

NASA Astrophysics Data System (ADS)

Mueller, W. F.; Bingham, C. R.; Reviol, W.; Riedinger, L. L.; Smith, B. H.; Wauters, J.; Ahmad, I.; Amro, H. A.; Blumenthal, D. J.; Carpenter, M. P.; Davids, C. N.; Fischer, S. M.; Hackman, G.; Henderson, D. J.; Janssens, R. V. F.; Khoo, T. L.; Lauritsen, T.; Lister, C. J.; Nisius, D. T.; Seweryniak, D.; Ma, W. C.

1996-05-01

High-spin states in ^179Au were studied for the first time in two experiments at the Argonne uc(atlas) facility. The ^144Sm(^40Ar,p4n)^179Au reaction at 207 MeV was used for the first experiment and ^124Te(^58Ni,p2n)^179Au at 255 MeV in the second. The setup in the first experiment consisted of the Fragment Mass Analyzer (uc(fma)) plus Parallel Plate Avalanche Counter (uc(ppac)) system and 10 Compton-suppressed Ge detectors (CSG's). From this run, several transitions from the yrast bands were established. The latter experiment utilized the uc(fma) + uc(ppac) system in conjunction with the uc(aye-ball) array of 19 Ge detectors (eight >70% efficient CSG's, nine 25% efficient CSG's, and two LEPS; one with Compton suppression) and a double sided silicon strip detector (uc(dssd).) The results from these experiments, including a level scheme, will be presented and discussed.

Infrared photodetectors based on graphene van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Ryzhii, V.; Ryzhii, M.; Svintsov, D.; Leiman, V.; Mitin, V.; Shur, M. S.; Otsuji, T.

2017-08-01

We propose and evaluate the graphene layer (GL) infrared photodetectors (GLIPs) based on the van der Waals (vdW) heterostructures with the radiation absorbing GLs. The operation of the GLIPs is associated with the electron photoexcitation from the GL valence band to the continuum states above the inter-GL barriers (either via tunneling or direct transitions to the continuum states). Using the developed device model, we calculate the photodetector characteristics as functions of the GL-vdW heterostructure parameters. We show that due to a relatively large efficiency of the electron photoexcitation and low capture efficiency of the electrons propagating over the barriers in the inter-GL layers, GLIPs should exhibit the elevated photoelectric gain and detector responsivity as well as relatively high detectivity. The possibility of high-speed operation, high conductivity, transparency of the GLIP contact layers, and the sensitivity to normally incident IR radiation provides additional potential advantages in comparison with other IR photodetectors. In particular, the proposed GLIPs can compete with unitravelling-carrier photodetectors.

Heralded wave packet manipulation and storage of a frequency-converted pair photon at telecom wavelength

NASA Astrophysics Data System (ADS)

Kroh, Tim; Ahlrichs, Andreas; Sprenger, Benjamin; Benson, Oliver

2017-09-01

Future quantum networks require a hybrid platform of dissimilar quantum systems. Within the platform, joint quantum states have to be mediated either by single photons, photon pairs or entangled photon pairs. The photon wavelength has to lie within the telecommunication band to enable long-distance fibre transmission. In addition, the temporal shape of the photons needs to be tailored to efficiently match the involved quantum systems. Altogether, this requires the efficient coherent wavelength-conversion of arbitrarily shaped single-photon wave packets. Here, we demonstrate the heralded temporal filtering of single photons as well as the synchronisation of state manipulation and detection as key elements in a typical experiment, besides of delaying a photon in a long fibre. All three are realised by utilising commercial telecommunication fibre-optical components which will permit the transition of quantum networks from the lab to real-world applications. The combination of these renders a temporally filtering single-photon storage in a fast switchable fibre loop possible.

A theoretical study of a series of water-soluble triphenylamine photosensitizers for two-photon photodynamic therapy.

PubMed

Wang, Xin; Yin, Xue; Lai, Xiao-Yong; Liu, Ying-Tao

2018-10-05

In this study, the therapeutic activity of a series of water-soluble triphenylamine (TP) photosensitizers (Ps) was explored by using theoretical simulations. The key photophysical parameters which determined the efficiency of Ps, such as absorption electronic spectra, singlet-triplet energy gaps and spin-orbit matrix elements were calculated at density functional theory and its time-dependent extension (DFT, TD-DFT). The calculated results showed that these TP photosensitizers possessed large two-photon absorption cross-section in the near-infrared region (NIR), efficient intersystem crossing (ISC) transition from the first singlet excited state to the low lying triplet excited states and sufficient energy for generating reactive oxygen species (ROS). These suitable features made these TP series holding great promise for applications in two-photon photodynamic therapy (PDT). These TP photosensitizers studied here in principle extended the application range of two-photon PDT in water solution. Copyright © 2018 Elsevier B.V. All rights reserved.

Preparing transition-metal clusters in known structural forms: the mass-analyzed threshold ionization spectrum of V3.

PubMed

Ford, Mark S; Mackenzie, Stuart R

2005-08-22

The first results are presented of a new experiment designed both to generate and characterize spectroscopically individual isomers of transition-metal cluster cations. As a proof of concept the one-photon mass-analyzed threshold ionization (MATI) spectrum of V3 has been recorded in the region of 44,000-45,000 cm-1. This study extends the range of a previous zero-kinetic-energy (ZEKE) photoelectron study of Yang et al. [Chem. Phys. Lett. 231, 177 (1994)] with which the current results are compared. The MATI spectra reported here exhibit surprisingly high resolution (0.2 cm-1) for this technique despite the use of large discrimination and extraction fields. Analysis of the rotational profile of the origin band allows assignment of the V3 ground state as and the V3+ ground state as , both with D3h geometry, in agreement with the density-functional theory study of the V3 ZEKE spectrum by Calaminici et al. [J. Chem. Phys. 114, 4036 (2001)]. There is also some evidence in the spectrum of transitions to the low-lying excited state of the ion. The vibrational structure observed in the MATI spectrum is, however, significantly different to and less extensive than that predicted in the density-functional theory study. Possible reasons for the discrepancies are discussed and an alternative assignment is proposed which results in revised values for the vibrational wave numbers of both the neutral and ionic states. These studies demonstrate the efficient generation of cluster ions in known structural (isomeric) forms and pave the way for the study of cluster reactivity as a function of geometrical structure.

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.

Progress towards a loophole-free test of nonlocality

NASA Astrophysics Data System (ADS)

McCusker, Kevin; Christensen, Bradley; Kwiat, Paul; Altepeter, Joseph

2012-02-01

We report on our progress towards a loophole-free test of nonlocality using spontaneous parametric down-conversion (SPDC). While the timing loophole can be easily closed in such a system by moving the detectors far apart [1], closing the detector loophole is significantly more difficult. In the standard Bell entangled states with the maximal violation of the CHSH inequality [2], an overall efficiency of 83% is required. This limit can be lowered to 67% by using non-maximally entangled states (although sensitivity to noise is greatly increased) [3]. We are carefully engineering our source to achieve maximal heralding efficiency, by optimizing both the spatial and spectral filtering, while keeping noise low using high-extinction-ratio polarizing beamsplitters. Combined with high-efficiency detectors, either optimized visible-light photon counters [4] or transition-edge sensors [5], closure of the detection loophole is within reach. [4pt] [1] G. Weihs et al., Phys. Rev. Lett. 81, 5039 (1998).[2] J. F. Clauser et al., Phys. Rev. Lett. 23, 880 (1969).[3] P.H. Eberhard, Phys. Rev. A 47, R747 (1993).[4] S. Takeuchi et al., Appl. Phys. Lett. 74, 1063 (1999).[5] A. E. Lita, A. J. Miller, and S. Nam, Opt. Exp. 16, 3032 (2008).

Chapter 8: Selective Stoichiometric and Catalytic Reactivity in the Confines of a Chiral Supramolecular Assembly

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

University of California, Berkeley; Lawrence Berkeley National Laboratory; Raymond, Kenneth

2007-09-27

Nature uses enzymes to activate otherwise unreactive compounds in remarkable ways. For example, DNases are capable of hydrolyzing phosphate diester bonds in DNA within seconds,[1-3]--a reaction with an estimated half-life of 200 million years without an enzyme.[4] The fundamental features of enzyme catalysis have been much discussed over the last sixty years in an effort to explain the dramatic rate increases and high selectivities of enzymes. As early as 1946, Linus Pauling suggested that enzymes must preferentially recognize and stabilize the transition state over the ground state of a substrate.[5] Despite the intense study of enzymatic selectivity and ability tomore » catalyze chemical reactions, the entire nature of enzyme-based catalysis is still poorly understood. For example, Houk and co-workers recently reported a survey of binding affinities in a wide variety of enzyme-ligand, enzyme-transition-state, and synthetic host-guest complexes and found that the average binding affinities were insufficient to generate many of the rate accelerations observed in biological systems.[6] Therefore, transition-state stabilization cannot be the sole contributor to the high reactivity and selectivity of enzymes, but rather, other forces must contribute to the activation of substrate molecules. Inspired by the efficiency and selectivity of Nature, synthetic chemists have admired the ability of enzymes to activate otherwise unreactive molecules in the confines of an active site. Although much less complex than the evolved active sites of enzymes, synthetic host molecules have been developed that can carry out complex reactions with their cavities. While progress has been made toward highly efficient and selective reactivity inside of synthetic hosts, the lofty goal of duplicating enzymes specificity remains.[7-9] Pioneered by Lehn, Cram, Pedersen, and Breslow, supramolecular chemistry has evolved well beyond the crown ethers and cryptands originally studied.[10-12] Despite the increased complexity of synthetic host molecules, most assembly conditions utilize self-assembly to form complex highly-symmetric structures from relatively simple subunits. For supramolecular assemblies able to encapsulate guest molecules, the chemical environment in each assembly--defined by the size, shape, charge, and functional group availability--greatly influences the guest-binding characteristics.[6, 13-17]« less

How active site protonation state influences the reactivity and ligation of the heme in chlorite dismutase

PubMed Central

Streit, Bennett R.; Blanc, Béatrice; Lukat-Rodgers, Gudrun S.; Rodgers, Kenton R.; DuBois, Jennifer L.

2010-01-01

Chlorite dismutase catalyzes O2 release from chlorite with exquisite efficiency and specificity. The spectroscopic properties, ligand binding affinities, and steady state kinetics of chlorite dismutase from Dechloromonas aromatica were examined over pH 3–11.5 to gain insight into how the protonation state of the heme environment influences dioxygen formation. An acid/base transition was observed by UV/visible and resonance Raman spectroscopy with a pKa of 8.7, 2–3 pH units below analogous transitions observed in typical His-ligated peroxidases. This transition marks the conversion of a five coordinate high spin Fe(III) to a mixed high/low spin ferric-hydroxide, as confirmed by resonance Raman (rR) spectroscopy. The two Fe–OH stretching frequencies are quite low, consistent with a weak Fe–OH bond, despite the nearly neutral imidazole side chain of the proximal histidine ligand. The hydroxide is proposed to interact strongly with a distal H-bond donor, thereby weakening the Fe–OH bond. The rR spectra of Cld-CO as a function of pH reveal two forms of the complex, one in which there is minimal interaction of distal residues with the carbonyl oxygen and another, acidic form in which the oxygen is under the influence of positive charge. Recent crystallographic data reveal arginine 183 as the lone H-bond donating residue in the distal pocket. It is likely that this Arg is the strong, positively charged H-bond donor implicated by vibrational data to interact with exogenous axial heme ligands. The same Arg in its neutral (pKa ~ 6.5) form also appears to act as the active site base in binding reactions of protonated ligands, such as HCN, to ferric Cld. The steady state profile for the rate of chlorite decomposition is characterized by these same pKas. The 5 coordinate high spin acidic Cld is more active than the alkaline hydroxide-bound form. The acid form decomposes chlorite most efficiently when the distal Arg is protonated/cationic (maximum kcat = 2.0 (±0.6) × 105 s−1, kcat/KM = 3.2 (±0.4) × 107 M−1s−1, pH 5.2, 4 °C) and to a somewhat lesser extent when it acts as a H-bond donor to the axial hydroxide ligand under alkaline conditions. PMID:20356038

Technologies for deposition of transition metal oxide thin films: application as functional layers in “Smart windows” and photocatalytic systems

NASA Astrophysics Data System (ADS)

Gesheva, K.; Ivanova, T.; Bodurov, G.; Szilágyi, I. M.; Justh, N.; Kéri, O.; Boyadjiev, S.; Nagy, D.; Aleksandrova, M.

2016-02-01

“Smart windows” are envisaged for future low-energy, high-efficient architectural buildings, as well as for the car industry. By switching from coloured to fully bleached state, these windows regulate the energy of solar flux entering the interior. Functional layers in these devices are the transition metals oxides. The materials (transitional metal oxides) used in smart windows can be also applied as photoelectrodes in water splitting photocells for hydrogen production or as photocatalytic materials for self-cleaning surfaces, waste water treatment and pollution removal. Solar energy utilization is recently in the main scope of numerous world research laboratories and energy organizations, working on protection against conventional fuel exhaustion. The paper presents results from research on transition metal oxide thin films, fabricated by different methods - atomic layer deposition, atmospheric pressure chemical vapour deposition, physical vapour deposition, and wet chemical methods, suitable for flowthrough production process. The lower price of the chemical deposition processes is especially important when the method is related to large-scale glazing applications. Conclusions are derived about which processes are recently considered as most prospective, related to electrochromic materials and devices manufacturing.

A new window towards multidimensional sensing of transition metal cations through dual mode sensing ability of N-benzyl-(3-hydoxy-2-naphthalene): emission enhancement coupled remarkable spectral shift.

PubMed

Paul, Bijan Kumar; Mahanta, Subrata; Singh, Rupashree Balia; Guchhait, Nikhil

2011-06-01

A structurally simple Schiff base N-benzyl-(3-hydroxy-2-naphthalene) (NBHN32) has been synthesized and characterized by (1)H NMR, (13)C NMR, and DEPT spectroscopy. The photophysical behaviour of NBHN32 in response to the presence of various transition metal cations has been explored by means of steady-state absorption, emission and time-resolved emission spectroscopy techniques. Efficient through space intramolecular photoinduced electron transfer (PET) between the naphthalene fluorophore and the imine group has been argued for extremely low fluorescence yield of NBHN32 compared to the parent molecule 3-hydroxy-2-naphthaldehyde (HN32) containing the same fluorophore but lacking the receptor moiety. Transition metal ion-induced emission enhancement is thus addressed on the lexicon of perturbation of the PET by the metal ions. Apart from fluorescence enhancement, transition metal ion imparts remarkable shift of the emission maxima of NBHN32, which is another unique aspect on the proposed ability of NBHN32 to function as a fluorescence chemosensor. Copyright © 2011 Elsevier B.V. All rights reserved.

Photo-induced reactions from efficient molecular dynamics with electronic transitions using the FIREBALL local-orbital density functional theory formalism.

PubMed

Zobač, Vladimír; Lewis, James P; Abad, Enrique; Mendieta-Moreno, Jesús I; Hapala, Prokop; Jelínek, Pavel; Ortega, José

2015-05-08

The computational simulation of photo-induced processes in large molecular systems is a very challenging problem. Firstly, to properly simulate photo-induced reactions the potential energy surfaces corresponding to excited states must be appropriately accessed; secondly, understanding the mechanisms of these processes requires the exploration of complex configurational spaces and the localization of conical intersections; finally, photo-induced reactions are probability events, that require the simulation of hundreds of trajectories to obtain the statistical information for the analysis of the reaction profiles. Here, we present a detailed description of our implementation of a molecular dynamics with electronic transitions algorithm within the local-orbital density functional theory code FIREBALL, suitable for the computational study of these problems. As an example of the application of this approach, we also report results on the [2 + 2] cycloaddition of ethylene with maleic anhydride and on the [2 + 2] photo-induced polymerization reaction of two C60 molecules. We identify different deactivation channels of the initial electron excitation, depending on the time of the electronic transition from LUMO to HOMO, and the character of the HOMO after the transition.

Liquid-vapor transition on patterned solid surfaces in a shear flow

NASA Astrophysics Data System (ADS)

Yao, Wenqi; Ren, Weiqing

2015-12-01

Liquids on a solid surface patterned with microstructures can exhibit the Cassie-Baxter (Cassie) state and the wetted Wenzel state. The transitions between the two states and the effects of surface topography, surface chemistry as well as the geometry of the microstructures on the transitions have been extensively studied in earlier work. However, most of these work focused on the study of the free energy landscape and the energy barriers. In the current work, we consider the transitions in the presence of a shear flow. We compute the minimum action path between the Wenzel and Cassie states using the minimum action method [W. E, W. Ren, and E. Vanden-Eijnden, Commun. Pure Appl. Math. 57, 637 (2004)]. Numerical results are obtained for transitions on a surface patterned with straight pillars. It is found that the shear flow facilitates the transition from the Wenzel state to the Cassie state, while it inhibits the transition backwards. The Wenzel state becomes unstable when the shear rate reaches a certain critical value. Two different scenarios for the Wenzel-Cassie transition are observed. At low shear rate, the transition happens via nucleation of the vapor phase at the bottom of the groove followed by its growth. At high shear rate, in contrary, the nucleation of the vapor phase occurs at the top corner of a pillar. The vapor phase grows in the direction of the flow, and the system goes through an intermediate metastable state before reaching the Cassie state.

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions.

PubMed

Zheng, Jingjing; Truhlar, Donald G

2012-01-01

Complex molecules often have many structures (conformations) of the reactants and the transition states, and these structures may be connected by coupled-mode torsions and pseudorotations; some but not all structures may have hydrogen bonds in the transition state or reagents. A quantitative theory of the reaction rates of complex molecules must take account of these structures, their coupled-mode nature, their qualitatively different character, and the possibility of merging reaction paths at high temperature. We have recently developed a coupled-mode theory called multi-structural variational transition state theory (MS-VTST) and an extension, called multi-path variational transition state theory (MP-VTST), that includes a treatment of the differences in the multi-dimensional tunneling paths and their contributions to the reaction rate. The MP-VTST method was presented for unimolecular reactions in the original paper and has now been extended to bimolecular reactions. The MS-VTST and MP-VTST formulations of variational transition state theory include multi-faceted configuration-space dividing surfaces to define the variational transition state. They occupy an intermediate position between single-conformation variational transition state theory (VTST), which has been used successfully for small molecules, and ensemble-averaged variational transition state theory (EA-VTST), which has been used successfully for enzyme kinetics. The theories are illustrated and compared here by application to three thermal rate constants for reactions of ethanol with hydroxyl radical--reactions with 4, 6, and 14 saddle points.

CellTrans: An R Package to Quantify Stochastic Cell State Transitions.

PubMed

Buder, Thomas; Deutsch, Andreas; Seifert, Michael; Voss-Böhme, Anja

2017-01-01

Many normal and cancerous cell lines exhibit a stable composition of cells in distinct states which can, e.g., be defined on the basis of cell surface markers. There is evidence that such an equilibrium is associated with stochastic transitions between distinct states. Quantifying these transitions has the potential to better understand cell lineage compositions. We introduce CellTrans, an R package to quantify stochastic cell state transitions from cell state proportion data from fluorescence-activated cell sorting and flow cytometry experiments. The R package is based on a mathematical model in which cell state alterations occur due to stochastic transitions between distinct cell states whose rates only depend on the current state of a cell. CellTrans is an automated tool for estimating the underlying transition probabilities from appropriately prepared data. We point out potential analytical challenges in the quantification of these cell transitions and explain how CellTrans handles them. The applicability of CellTrans is demonstrated on publicly available data on the evolution of cell state compositions in cancer cell lines. We show that CellTrans can be used to (1) infer the transition probabilities between different cell states, (2) predict cell line compositions at a certain time, (3) predict equilibrium cell state compositions, and (4) estimate the time needed to reach this equilibrium. We provide an implementation of CellTrans in R, freely available via GitHub (https://github.com/tbuder/CellTrans).

Role of entropy and structural parameters in the spin-state transition of LaCoO3

NASA Astrophysics Data System (ADS)

Chakrabarti, Bismayan; Birol, Turan; Haule, Kristjan

2017-11-01

The spin-state transition in LaCoO3 has eluded description for decades despite concerted theoretical and experimental effort. In this study, we approach this problem using fully charge self-consistent density functional theory + embedded dynamical mean field theory (DFT+DMFT). We show from first principles that LaCoO3 cannot be described by a single, pure spin state at any temperature. Instead, we observe a gradual change in the population of higher-spin multiplets with increasing temperature, with the high-spin multiplets being excited at the onset of the spin-state transition followed by the intermediate-spin multiplets being excited at the metal-insulator-transition temperature. We explicitly elucidate the critical role of lattice expansion and oxygen octahedral rotations in the spin-state transition. We also reproduce, from first principles, that the spin-state transition and the metal-insulator transition in LaCoO3 occur at different temperature scales. In addition, our results shed light on the importance of electronic entropy in driving the spin-state transition, which has so far been ignored in all first-principles studies of this material.

Energy Landscape and Transition State of Protein-Protein Association

NASA Astrophysics Data System (ADS)

Alsallaq, Ramzi; Zhou, Huan-Xiang

2006-11-01

Formation of a stereospecific protein complex is favored by specific interactions between two proteins but disfavored by the loss of translational and rotational freedom. Echoing the protein folding process, we have previously proposed a transition state for protein-protein association. Here we clarify the specification of the transition state by working with two toy models for protein association. The models demonstrate that a sharp transition between the bound state with numerous short-range interactions but restricted translation and rotational freedom and the unbound state with at most a small number of interactions but expanded configurational freedom. This transition sets the outer boundary of the bound state as well as the transition state for association. The energy landscape is funnel-like, with the deep well of the bound state surrounded by a broad shallow basin. This formalism of protein-protein association is applied to four protein-protein complexes, and is found to give accurate predictions for the effects of charge mutations and ionic strength on the association rates.

Hybrid Turbine Electric Vehicle

NASA Technical Reports Server (NTRS)

Viterna, Larry A.

1997-01-01

Hybrid electric power trains may revolutionize today's ground passenger vehicles by significantly improving fuel economy and decreasing emissions. The NASA Lewis Research Center is working with industry, universities, and Government to develop and demonstrate a hybrid electric vehicle. Our partners include Bowling Green State University, the Cleveland Regional Transit Authority, Lincoln Electric Motor Division, the State of Ohio's Department of Development, and Teledyne Ryan Aeronautical. The vehicle will be a heavy class urban transit bus offering double the fuel economy of today's buses and emissions that are reduced to 1/10th of the Environmental Protection Agency's standards. At the heart of the vehicle's drive train is a natural-gas-fueled engine. Initially, a small automotive engine will be tested as a baseline. This will be followed by the introduction of an advanced gas turbine developed from an aircraft jet engine. The engine turns a high-speed generator, producing electricity. Power from both the generator and an onboard energy storage system is then provided to a variable-speed electric motor attached to the rear drive axle. An intelligent power-control system determines the most efficient operation of the engine and energy storage system.

A simple resonance enhanced laser ionization scheme for CO via the A1Π state

NASA Astrophysics Data System (ADS)

Sun, Z. F.; von Zastrow, A. D.; Parker, D. H.

2017-07-01

We investigate the laser ionization process taking place when the CO molecule is exposed to vacuum ultraviolet (VUV) radiation resonant with the CO A1Π (v = 0) ← X1Σ+ (v = 0) transition around 154 nm, along with the ultraviolet (UV) and visible (Red) radiation used to generate VUV by four-wave difference-frequency mixing. By measuring the CO+ ion recoil and a room temperature gas spectrum, it is possible to assign the ionization process as 1 + 1' + 1'' REMPI where the one-photon steps refer to the VUV, UV, and Red radiation, respectively. Resonance enhanced ionization of rotational states around J = 12 arise due to the overlap of the fixed wavelength UV (˜250 nm) with the R band-head of a transition assigned to CO E1Π (v = 6) ← A1Π (v = 0) with a term value of 104 787.5 cm-1. The REMPI process is efficient and polarization sensitive and should be useful in a wide range of studies involving nascent CO.

Design of three-well indirect pumping terahertz quantum cascade lasers for high optical gain based on nonequilibrium Green's function analysis

NASA Astrophysics Data System (ADS)

Liu, Tao; Kubis, Tillmann; Jie Wang, Qi; Klimeck, Gerhard

2012-03-01

The nonequilibrium Green's function approach is applied to the design of three-well indirect pumping terahertz (THz) quantum cascade lasers (QCLs) based on a resonant phonon depopulation scheme. The effects of the anticrossing of the injector states and the dipole matrix element of the laser levels on the optical gain of THz QCLs are studied. The results show that a design that results in a more pronounced anticrossing of the injector states will achieve a higher optical gain in the indirect pumping scheme compared to the traditional resonant-tunneling injection scheme. This offers in general a more efficient coherent resonant-tunneling transport of electrons in the indirect pumping scheme. It is also shown that, for operating temperatures below 200 K and low lasing frequencies, larger dipole matrix elements, i.e., vertical optical transitions, offer a higher optical gain. In contrast, in the case of high lasing frequencies, smaller dipole matrix elements, i.e., diagonal optical transitions are better for achieving a higher optical gain.

Non-statistical effects in bond fission reactions of 1,2-difluoroethane

NASA Astrophysics Data System (ADS)

Schranz, Harold W.; Raff, Lionel M.; Thompson, Donald L.

1991-08-01

A microcanonical, classical variational transition-state theory based on the use of the efficient microcanonical sampling (EMS) procedure is applied to simple bond fission in 1,2-difluoroethane. Comparison is made with results of trajectory calculations performed on the same global potential-energy surface. Agreement between the statistical theory and trajectory results for CC CF and CH bond fissions is poor with differences as large as a factor of 125. Most importantly, at the lower energy studied, 6.0 eV, the statistical calculations predict considerably slower rates than those computed from trajectories. We conclude from these results that the statistical assumptions inherent in the transition-state theory method are not valid for 1,2-difluoroethane in spite of the fact that the total intramolecular energy transfer rate out of CH and CC normal and local modes is large relative to the bond fission rates. The IVR rate is not globally rapid and the trajectories do not access all of the energetically available phase space uniformly on the timescale of the reactions.

Vibrational self-consistent field theory using optimized curvilinear coordinates.

PubMed

Bulik, Ireneusz W; Frisch, Michael J; Vaccaro, Patrick H

2017-07-28

A vibrational SCF model is presented in which the functions forming the single-mode functions in the product wavefunction are expressed in terms of internal coordinates and the coordinates used for each mode are optimized variationally. This model involves no approximations to the kinetic energy operator and does not require a Taylor-series expansion of the potential. The non-linear optimization of coordinates is found to give much better product wavefunctions than the limited variations considered in most previous applications of SCF methods to vibrational problems. The approach is tested using published potential energy surfaces for water, ammonia, and formaldehyde. Variational flexibility allowed in the current ansätze results in excellent zero-point energies expressed through single-product states and accurate fundamental transition frequencies realized by short configuration-interaction expansions. Fully variational optimization of single-product states for excited vibrational levels also is discussed. The highlighted methodology constitutes an excellent starting point for more sophisticated treatments, as the bulk characteristics of many-mode coupling are accounted for efficiently in terms of compact wavefunctions (as evident from the accurate prediction of transition frequencies).

The multiuniverse transition in superfluid 3He

NASA Astrophysics Data System (ADS)

Bunkov, Yury

2013-10-01

The symmetry-breaking phase transitions of the universe and of superfluid 3He may lead to the formation of different states with different order parameters. In both cases the energy potential below the transition temperature has a complicated multidimensional profile with many local minima and saddle points, which correspond to different states. Consequently, not only topological defects, but also islands of different metastable states can be created. Using 3He we can analyse the properties and experimental consequences of such transitions and, in particular, the first-order phase transition between the two low symmetry states.

The multiuniverse transition in superfluid 3He.

PubMed

Bunkov, Yury

2013-10-09

The symmetry-breaking phase transitions of the universe and of superfluid (3)He may lead to the formation of different states with different order parameters. In both cases the energy potential below the transition temperature has a complicated multidimensional profile with many local minima and saddle points, which correspond to different states. Consequently, not only topological defects, but also islands of different metastable states can be created. Using (3)He we can analyse the properties and experimental consequences of such transitions and, in particular, the first-order phase transition between the two low symmetry states.

Extracting rate coefficients from single-molecule photon trajectories and FRET efficiency histograms for a fast-folding protein.

PubMed

Chung, Hoi Sung; Gopich, Irina V; McHale, Kevin; Cellmer, Troy; Louis, John M; Eaton, William A

2011-04-28

Recently developed statistical methods by Gopich and Szabo were used to extract folding and unfolding rate coefficients from single-molecule Förster resonance energy transfer (FRET) data for proteins with kinetics too fast to measure waiting time distributions. Two types of experiments and two different analyses were performed. In one experiment bursts of photons were collected from donor and acceptor fluorophores attached to a 73-residue protein, α(3)D, freely diffusing through the illuminated volume of a confocal microscope system. In the second, the protein was immobilized by linkage to a surface, and photons were collected until one of the fluorophores bleached. Folding and unfolding rate coefficients and mean FRET efficiencies for the folded and unfolded subpopulations were obtained from a photon by photon analysis of the trajectories using a maximum likelihood method. The ability of the method to describe the data in terms of a two-state model was checked by recoloring the photon trajectories with the extracted parameters and comparing the calculated FRET efficiency histograms with the measured histograms. The sum of the rate coefficients for the two-state model agreed to within 30% with the relaxation rate obtained from the decay of the donor-acceptor cross-correlation function, confirming the high accuracy of the method. Interestingly, apparently reliable rate coefficients could be extracted using the maximum likelihood method, even at low (<10%) population of the minor component where the cross-correlation function was too noisy to obtain any useful information. The rate coefficients and mean FRET efficiencies were also obtained in an approximate procedure by simply fitting the FRET efficiency histograms, calculated by binning the donor and acceptor photons, with a sum of three-Gaussian functions. The kinetics are exposed in these histograms by the growth of a FRET efficiency peak at values intermediate between the folded and unfolded peaks as the bin size increases, a phenomenon with similarities to NMR exchange broadening. When comparable populations of folded and unfolded molecules are present, this method yields rate coefficients in very good agreement with those obtained with the maximum likelihood method. As a first step toward characterizing transition paths, the Viterbi algorithm was used to locate the most probable transition points in the photon trajectories.

The vacuum ultraviolet spectrum of krypton and xenon excimers excited in a cooled dc discharge

NASA Astrophysics Data System (ADS)

Gerasimov, G.; Krylov, B.; Loginov, A.; Zvereva, G.; Hallin, R.; Arnesen, A.; Heijkenskjöld, F.

1998-01-01

We present results of an experimental and theoretical study of the VUV spectra of krypton and xenon excimers excited by a dc discharge in a capillary tube cooled by liquid nitrogen. The studied spectral regions of 115-170 nm and 140-195 nm for krypton and xenon respectively correspond to transitions between the lowest excited dimer states 1u, 0u+ and the weakly bound ground state 0g+. A semiempirical method was suggested and applied to describe the experimental spectra and to estimate the temperature of the radiating plasma volume. Electron impact, transferring dimers from the ground state to the excited states, is shown to be an efficient excitation mechanism in the 100-850 hPa and the 10-50 mA pressure and discharge current ranges. The spectra obtained as well as the results of calculations corroborate the high rate of this mechanism.

Effect of solvent hydrogen bonding on the photophysical properties of intramolecular charge transfer probe trans-ethyl p-(dimethylamino) cinamate and its derivative

NASA Astrophysics Data System (ADS)

Singh, T. Sanjoy; Moyon, N. S.; Mitra, Sivaprasad

2009-08-01

Intramolecular charge transfer (ICT) behavior of trans-ethyl p-(dimethylamino) cinamate (EDAC) and 4-(dimethylamino) cinnamic acid (DMACA) were studied by steady state absorption and emission, picosecond time-resolved fluorescence experiments in various pure and mixed solvent systems. The large fluorescence spectral shift in more polar solvents indicates an efficient charge transfer from the donor site to the acceptor moiety in the excited state compared to the ground state. The energy for 0,0 transition ( ν0,0) for EDAC shows very good linear correlation with static solvent dielectric property; however, fluorescence emission maximum, stokes shift and fluorescence quantum yield show significant deviation from linearity in polar protic solvents, indicating a large contribution of solvent hydrogen bonding on the excited state relaxation mechanism. A quantitative estimation of contribution from different solvatochromic parameters was made using linear free energy relationship based on Kamlet-Taft equation.

Donor-σ-Acceptor Motifs: Thermally Activated Delayed Fluorescence Emitters with Dual Upconversion.

PubMed

Geng, Yan; D'Aleo, Anthony; Inada, Ko; Cui, Lin-Song; Kim, Jong Uk; Nakanotani, Hajime; Adachi, Chihaya

2017-12-22

A family of organic emitters with a donor-σ-acceptor (D-σ-A) motif is presented. Owing to the weakly coupled D-σ-A intramolecular charge-transfer state, a transition from the localized excited triplet state ( 3 LE) and charge-transfer triplet state ( 3 CT) to the charge-transfer singlet state ( 1 CT) occurred with a small activation energy and high photoluminescence quantum efficiency. Two thermally activated delayed fluorescence (TADF) components were identified, one of which has a very short lifetime of 200-400 ns and the other a longer TADF lifetime of the order of microseconds. In particular, the two D-σ-A materials presented strong blue emission with TADF properties in toluene. These results will shed light on the molecular design of new TADF emitters with short delayed lifetimes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Demonstrating an Order-of-Magnitude Sampling Enhancement in Molecular Dynamics Simulations of Complex Protein Systems.

PubMed

Pan, Albert C; Weinreich, Thomas M; Piana, Stefano; Shaw, David E

2016-03-08

Molecular dynamics (MD) simulations can describe protein motions in atomic detail, but transitions between protein conformational states sometimes take place on time scales that are infeasible or very expensive to reach by direct simulation. Enhanced sampling methods, the aim of which is to increase the sampling efficiency of MD simulations, have thus been extensively employed. The effectiveness of such methods when applied to complex biological systems like proteins, however, has been difficult to establish because even enhanced sampling simulations of such systems do not typically reach time scales at which convergence is extensive enough to reliably quantify sampling efficiency. Here, we obtain sufficiently converged simulations of three proteins to evaluate the performance of simulated tempering, a member of a widely used class of enhanced sampling methods that use elevated temperature to accelerate sampling. Simulated tempering simulations with individual lengths of up to 100 μs were compared to (previously published) conventional MD simulations with individual lengths of up to 1 ms. With two proteins, BPTI and ubiquitin, we evaluated the efficiency of sampling of conformational states near the native state, and for the third, the villin headpiece, we examined the rate of folding and unfolding. Our comparisons demonstrate that simulated tempering can consistently achieve a substantial sampling speedup of an order of magnitude or more relative to conventional MD.

Is steady-state capitalism viable? A review of the issues and an answer in the affirmative.

PubMed

Lawn, Philip

2011-02-01

Most ecological economists believe that the transition to a steady-state economy is necessary to ensure ecological sustainability and to maximize a nation's economic welfare. While some observers agree with the necessity of the steady-state economy, they are nonetheless critical of the suggestion made by ecological economists-in particular, Herman Daly-that a steady-state economy is compatible with a capitalist system. First, they believe that steady-state capitalism is based on the untenable assumption that growth is an optional rather than in-built element of capitalism. Second, they argue that capitalist notions of efficient resource allocation are too restrictive to facilitate the transition to an "ecological" or steady-state economy. I believe these observers are outright wrong with their first criticism and, because they misunderstand Daly's vision of a steady-state economy, are misplaced with their second criticism. The nature of a capitalist system depends upon the institutional framework that supports and shapes it. Hence, a capitalist system can exist in a wide variety of forms. Unfortunately, many observers fail to recognize that the current "growth imperative" is the result of capitalist systems everywhere being institutionally designed to grow. They need not be designed this way to survive and thrive. Indeed, because continued growth is both existentially undesirable and ecologically unsustainable, redesigning capitalist systems through the introduction of Daly-like institutions would prove to be capitalism's savior. What's more, it would constitute humankind's best hope of achieving sustainable development. © 2011 New York Academy of Sciences.

Quantum Monte Carlo calculations of electromagnetic transitions in $^8$Be with meson-exchange currents derived from chiral effective field theory

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

Pastore, S.; Wiringa, Robert B.; Pieper, Steven C.

2014-08-01

We report quantum Monte Carlo calculations of electromagnetic transitions inmore » $^8$Be. The realistic Argonne $$v_{18}$$ two-nucleon and Illinois-7 three-nucleon potentials are used to generate the ground state and nine excited states, with energies that are in excellent agreement with experiment. A dozen $M1$ and eight $E2$ transition matrix elements between these states are then evaluated. The $E2$ matrix elements are computed only in impulse approximation, with those transitions from broad resonant states requiring special treatment. The $M1$ matrix elements include two-body meson-exchange currents derived from chiral effective field theory, which typically contribute 20--30\\% of the total expectation value. Many of the transitions are between isospin-mixed states; the calculations are performed for isospin-pure states and then combined with the empirical mixing coefficients to compare to experiment. In general, we find that transitions between states that have the same dominant spatial symmetry are in decent agreement with experiment, but those transitions between different spatial symmetries are often significantly underpredicted.« less

The folding transition state of Protein L is extensive with non-native interactions (and not small and polarized)

PubMed Central

Yoo, Tae Yeon; Adhikari, Aashish; Xia, Zhen; Huynh, Tien; Freed, Karl F.; Zhou, Ruhong; Sosnick, Tobin R.

2012-01-01

Progress in understanding protein folding relies heavily upon an interplay between experiment and theory. In particular, readily interpretable experimental data are required that can be meaningfully compared to simulations. According to standard mutational φ analysis, the transition state for Protein L contains only a single hairpin. However, we demonstrate here using ψ analysis with engineered metal ion binding sites that the transition state is extensive, containing the entire four-stranded β sheet. Underreporting of the structural content of the transition state by φ analysis also occurs for acyl phosphatase1, ubiquitin2 and BdpA3. The carboxy terminal hairpin in the transition state of Protein L is found to be non-native, a significant result that agrees with our PDB-based backbone sampling and all-atom simulations. The non-native character partially explains the failure of accepted experimental and native-centric computational approaches to adequately describe the transition state. Hence, caution is required even when an apparent agreement exists between experiment and theory, thus highlighting the importance of having alternative methods for characterizing transition states. PMID:22522126

Epitaxial strain-mediated spin-state transitions: can we switch off magnetism?

NASA Astrophysics Data System (ADS)

Rondinelli, James; Spaldin, Nicola

2008-03-01

We use first-principles density functional theory calculations to explore spin-state transitions in epitaxially strained LaCoO3. While high-spin to low-spin state transitions in minerals are common in geophysics, where pressures can reach over 200 GPa, we explore whether heteroepitaxial strain can achieve similar transitions with moderate strain in thin films. LaCoO3 is known to undergo a low-spin (S=0, t2g^6eg^0) to intermediate-spin (S=1, t2g^5eg^1) or high-spin (S=2, t2g^4eg^2) state transition with increasing temperature, and thus makes it a promising candidate material for strain-mediated spin transitions. Here we discuss the physics of the low-spin transition and changes in the electronic structure of LaCoO3, most notably, the metal-insulator transition that accompanies the spin-state transitions with epitaxial strain. As thin film growth techniques continue to reach atomic-level precision, we suggest this is another approach for controlling magnetism in complex oxide heterostructures.

Resonant transition-based quantum computation

NASA Astrophysics Data System (ADS)

Chiang, Chen-Fu; Hsieh, Chang-Yu

2017-05-01

In this article we assess a novel quantum computation paradigm based on the resonant transition (RT) phenomenon commonly associated with atomic and molecular systems. We thoroughly analyze the intimate connections between the RT-based quantum computation and the well-established adiabatic quantum computation (AQC). Both quantum computing frameworks encode solutions to computational problems in the spectral properties of a Hamiltonian and rely on the quantum dynamics to obtain the desired output state. We discuss how one can adapt any adiabatic quantum algorithm to a corresponding RT version and the two approaches are limited by different aspects of Hamiltonians' spectra. The RT approach provides a compelling alternative to the AQC under various circumstances. To better illustrate the usefulness of the novel framework, we analyze the time complexity of an algorithm for 3-SAT problems and discuss straightforward methods to fine tune its efficiency.

Ionization cross section, pressure shift and isotope shift measurements of osmium

NASA Astrophysics Data System (ADS)

Hirayama, Yoshikazu; Mukai, Momo; Watanabe, Yutaka; Oyaizu, Michihiro; Ahmed, Murad; Kakiguchi, Yutaka; Kimura, Sota; Miyatake, Hiroari; Schury, Peter; Wada, Michiharu; Jeong, Sun-Chan

2017-11-01

In-gas-cell laser resonance ionization spectroscopy of neutral osmium atoms was performed with the use of a two-color two-step laser resonance ionization technique. Saturation curves for the ionization scheme were measured, and the ionization cross section was experimentally determined by solving the rate equations for the ground, intermediate and ionization continuum populations. The pressure shift and pressure broadening in the resonance spectra of the excitation transition were measured. The electronic factor {F}247 for the transition {λ }1=247.7583 nm to the intermediate state was deduced from the measured isotope shifts of stable {}{188,189,{190,192}}Os isotopes. The efficient ionization scheme, pressure shift, nuclear isotope shift and {F}247 are expected to be useful for applications of laser ion sources to unstable nuclei and for nuclear spectroscopy based on laser ionization techniques.

Impact of zeolite-Y framework on the geometry and reactivity of Ru (III) benzimidazole complexes - A DFT study

NASA Astrophysics Data System (ADS)

Selvaraj, Tamilmani; Rajalingam, Renganathan; Balasubramanian, Viswanathan

2018-03-01

A detailed comparative Density Functional Theory (DFT) study is made to understand the structural changes of the guest complex due to steric and electronic interactions with the host framework. In this study, Ru(III) benzimidazole and 2- ethyl Ru(III) benzimidazole complexes encapsulated in a supercage of zeolite Y. The zeolitic framework integrity is not disturbed by the intrusion of the large guest complex. A blue shift in the d-d transition observed in the UV-Visible spectroscopic studies of the zeolite encapsulated complexes and they shows a higher catalytic efficiency. Encapsulation of zeolite matrix makes the metal center more viable to nucleophilic attack and favors the phenol oxidation reaction. Based on the theoretical calculations, transition states and structures of reaction intermediates involved in the catalytic cycles are derived.

Near-optimal energy transitions for energy-state trajectories of hypersonic aircraft

NASA Technical Reports Server (NTRS)

Ardema, M. D.; Bowles, J. V.; Terjesen, E. J.; Whittaker, T.

1992-01-01

A problem of the instantaneous energy transition that occurs in energy-state approximation is considered. The transitions are modeled as a sequence of two load-factor bounded paths (either climb-dive or dive-climb). The boundary-layer equations associated with the energy-state dynamic model are analyzed to determine the precise location of the transition.

Initial Conceptualization and Application of the Alaska Thermokarst Model

NASA Astrophysics Data System (ADS)

Bolton, W. R.; Lara, M. J.; Genet, H.; Romanovsky, V. E.; McGuire, A. D.

2015-12-01

Thermokarst topography forms whenever ice-rich permafrost thaws and the ground subsides due to the volume loss when ground ice transitions to water. The Alaska Thermokarst Model (ATM) is a large-scale, state-and-transition model designed to simulate transitions between landscape units affected by thermokarst disturbance. The ATM uses a frame-based methodology to track transitions and proportion of cohorts within a 1-km2 grid cell. In the arctic tundra environment, the ATM tracks thermokarst-related transitions among wetland tundra, graminoid tundra, shrub tundra, and thermokarst lakes. In the boreal forest environment, the ATM tracks transitions among forested permafrost plateau, thermokarst lakes, collapse scar fens and bogs. The transition from one cohort to another due to thermokarst processes can take place if thaw reaches ice-rich ground layers either due to pulse disturbance (i.e. large precipitation event or fires), or due to gradual active layer deepening that eventually results in penetration of the protective layer. The protective layer buffers the ice-rich soils from the land surface and is critical to determine how susceptible an area is to thermokarst degradation. The rate of terrain transition in our model is determined by a set of rules that are based upon the ice-content of the soil, the drainage efficiency (or the ability of the landscape to store or transport water), the cumulative probability of thermokarst initiation, distance from rivers, lake dynamics (increasing, decreasing, or stable), and other factors. Tundra types are allowed to transition from one type to another (for example, wetland tundra to graminoid tundra) under favorable climatic conditions. In this study, we present our conceptualization and initial simulation results from in the arctic (the Barrow Peninsula) and boreal (the Tanana Flats) regions of Alaska.

High efficiency trucks : new revenues, new jobs, and improved fuel economy in the medium and heavy truck fleet.

DOT National Transportation Integrated Search

2010-05-01

The move to high efficiency trucks can lead to new revenues and jobs for companies involved in the development and marketing of the technologies needed to make this transition. But in order for the medium and heavy truck industry to make this transit...

Methodology for modeling the microbial contamination of air filters.

PubMed

Joe, Yun Haeng; Yoon, Ki Young; Hwang, Jungho

2014-01-01

In this paper, we propose a theoretical model to simulate microbial growth on contaminated air filters and entrainment of bioaerosols from the filters to an indoor environment. Air filter filtration and antimicrobial efficiencies, and effects of dust particles on these efficiencies, were evaluated. The number of bioaerosols downstream of the filter could be characterized according to three phases: initial, transitional, and stationary. In the initial phase, the number was determined by filtration efficiency, the concentration of dust particles entering the filter, and the flow rate. During the transitional phase, the number of bioaerosols gradually increased up to the stationary phase, at which point no further increase was observed. The antimicrobial efficiency and flow rate were the dominant parameters affecting the number of bioaerosols downstream of the filter in the transitional and stationary phase, respectively. It was found that the nutrient fraction of dust particles entering the filter caused a significant change in the number of bioaerosols in both the transitional and stationary phases. The proposed model would be a solution for predicting the air filter life cycle in terms of microbiological activity by simulating the microbial contamination of the filter.

A spin transition mechanism for cooperative adsorption in metal-organic frameworks

NASA Astrophysics Data System (ADS)

Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia; Mason, Jarad A.; Runčevski, Tomče; Xiao, Dianne J.; Darago, Lucy E.; Crocellà, Valentina; Bordiga, Silvia; Long, Jeffrey R.

2017-10-01

Cooperative binding, whereby an initial binding event facilitates the uptake of additional substrate molecules, is common in biological systems such as haemoglobin. It was recently shown that porous solids that exhibit cooperative binding have substantial energetic benefits over traditional adsorbents, but few guidelines currently exist for the design of such materials. In principle, metal-organic frameworks that contain coordinatively unsaturated metal centres could act as both selective and cooperative adsorbents if guest binding at one site were to trigger an electronic transformation that subsequently altered the binding properties at neighbouring metal sites. Here we illustrate this concept through the selective adsorption of carbon monoxide (CO) in a series of metal-organic frameworks featuring coordinatively unsaturated iron(II) sites. Functioning via a mechanism by which neighbouring iron(II) sites undergo a spin-state transition above a threshold CO pressure, these materials exhibit large CO separation capacities with only small changes in temperature. The very low regeneration energies that result may enable more efficient Fischer-Tropsch conversions and extraction of CO from industrial waste feeds, which currently underutilize this versatile carbon synthon. The electronic basis for the cooperative adsorption demonstrated here could provide a general strategy for designing efficient and selective adsorbents suitable for various separations.

Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

PubMed

Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

2017-10-09

Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH 4 ) n [MMo 6 O 18 (OH) 6 ] (M=Cu 2+ ; Fe 3+ ; Co 3+ ; Ni 2+ ; Zn 2+ , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O 2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo VI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO 6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular Level Understanding of Sodium Dodecyl Sulfate (SDS) Induced Sol-Gel Transition of Pluronic F127 Using Fisetin as a Fluorescent Molecular Probe.

PubMed

Mishra, Jhili; Swain, Jitendriya; Mishra, Ashok Kumar

2018-01-11

The thermoreversible sol-gel transition of pluronic F127 is markedly altered even with addition of submicellar concentration of sodium dodecyl sulfate (SDS) surfactant. Multiple fluorescence parameters like fluorescence intensity, fluorescence anisotropy and fluorescence lifetime of both the prototropic forms (anion (A - *) and phototautomer FT*) of the photoprototropic fluorescent probe fisetin has been efficiently used to understand the molecular level properties like polarity and microviscosity of the PF127-SDS system as a function of temperature. The SDS-induced increase in the interfacial hydrophobicity level is seen to affect the sol-gel phase transition of PF127 (21-18 °C). The E T (30) polarity parameter value of anionic emission of fisetin suggests that there is a considerable decrease in the polarity of the PF127 medium with increase in temperature and with the addition of SDS. The microviscosity progressively increases from ∼5 mPa s (sol state, 10 °C) to ∼22.01 mPa s (gel state 35 °C) in aqueous solution of PF127. The variation in microviscosity with addition of SDS in PF127-SDS mixed system is significant in sol phase whereas in gel phase this variation is significantly less. Temperature dependent fluorescence lifetime of FT* indicates that there is heterogeneity in distribution of fisetin molecules at different domains of PF127. This work also show-cases the sensitivity of fisetin toward change in polarity and change in sol-gel transition temperature of copolymer PF127 with variation in temperature (both forward and reverse directions) and SDS.

Arginine Coordination in Enzymatic Phosphoryl Transfer: Evaluation of the Effect of Arg166 Mutations in Escherichia Coli Alkaline Phosphatase

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

O'Brien, P.J.; Lassila, J.K.; Fenn, T.D.

2009-05-22

Arginine residues are commonly found in the active sites of enzymes catalyzing phosphoryl transfer reactions. Numerous site-directed mutagenesis experiments establish the importance of these residues for efficient catalysis, but their role in catalysis is not clear. To examine the role of arginine residues in the phosphoryl transfer reaction, we have measured the consequences of mutations to arginine 166 in Escherichia coli alkaline phosphatase on hydrolysis of ethyl phosphate, on individual reaction steps in the hydrolysis of the covalent enzyme-phosphoryl intermediate, and on thio substitution effects. The results show that the role of the arginine side chain extends beyond its positivemore » charge, as the Arg166Lys mutant is as compromised in activity as Arg166Ser. Through measurement of individual reaction steps, we construct a free energy profile for the hydrolysis of the enzyme-phosphate intermediate. This analysis indicates that the arginine side chain strengthens binding by {approx}3 kcal/mol and provides an additional 1-2 kcal/mol stabilization of the chemical transition state. A 2.1 {angstrom} X-ray diffraction structure of Arg166Ser AP is presented, which shows little difference in enzyme structure compared to the wild-type enzyme but shows a significant reorientation of the bound phosphate. Altogether, these results support a model in which the arginine contributes to catalysis through binding interactions and through additional transition state stabilization that may arise from complementarity of the guanidinum group to the geometry of the trigonal bipyramidal transition state.« less

Is the atmosphere of the extremely irradiated exoplanet WASP-43b in a blow-off state?

NASA Astrophysics Data System (ADS)

Pino, Lorenzo

2016-10-01

In the past months we have obtained evidence that an unusual phenomenon is happening in the atmosphere of one of the Hot Jupiters with shortest period. High-resolution spectroscopy from the ground reveals a transit spectrum where the sodium absorption signal from the planet peaks at 2-3%, which is larger than the planet transit depth in white light and 100 times larger than the well HST-established detection of sodium in HD 209458b (Charbonneau et al. 2002). Only in the UV have such large signatures been observed, for lighter hydrogen, carbon and oxygen atoms being blown-off by hydrodynamical atmospheric escape. So far, sodium atoms have never been observed higher than the thermosphere, where they should get promptly ionized.Analysis of ground-based data is challenging because the spectroscopic signatures can be mimicked by the Earth atmosphere, and a sophisticated removal of telluric contamination is necessary. Our observations show that an efficient telluric correction for this target, particularly faint in the sodium region, is impossible, making a space-based confirmation necessary. In a single transit, HST/STIS could obtain a 5-sigma confirmation of the signal. This detection would unambiguously show that the planetary atmosphere is in a state of extreme blow-off, with large exospheric densities allowing for a high recombination rate able to maintain sodium in a neutral state even high up in the atmosphere. This would represent the first constraint on atmospheric evaporation obtained in the optical, and would thus open a new, UV-independent path to the characterization of evaporating atmospheres, crucial in the post-HST era.

Graphene-based vdW heterostructure Induced High-efficiency Thermoelectric Devices

NASA Astrophysics Data System (ADS)

Liang, Shijun; Ang, Lay Kee

Thermoelectric material (TE) can convert the heat into electricity to provide green energy source and its performance is characterized by a figure of merit (ZT) parameter. Traditional TE materials only give ZT equal to around 1 at room temperature. But, it is believed that materials with ZT >3 will find wide applications at this low temperature range. Prior studies have implied that the interrelation between electric conductivity and lattice thermal conductivity renders the goal of engineering ZT of bulk materials to reach ZT >3. In this work, we propose a high-efficiency van del Waals (vdW) heterostructure-based thermionic device with graphene electrodes, which is able to harvest wasted heat (around 400K) based on the newly established thermionic emission law of graphene electrodes instead of Seebeck effect, to boost the efficiency of power generation over 10% around room temperature. The efficiency can be above 20% if the Schottky barrier height and cross-plane lattice thermal conductivity of transition metal dichacogenides (TMD) materials can be fine-engineered. As a refrigerator at 260 K, the efficiency is 50% to 80% of Carnot efficiency. Finally, we identify two TMD materials as the ideal candidates of graphene/TMD/graphene devices based on the state-of-art technology.

Youth and administrator perspectives on transition in Kentucky's state agency schools.

PubMed

Marshall, Amy; Powell, Norman; Pierce, Doris; Nolan, Ronnie; Fehringer, Elaine

2012-01-01

Students, a large percentage with disabilities, are at high risk for poor post-secondary outcomes in state agency education programs. This mixed-methods study describes the understandings of student transitions in state agency education programs from the perspectives of youth and administrators. Results indicated that: transition is more narrowly defined within alternative education programs; key strengths of transition practice are present in nontraditional schools; and the coordination barriers within this fluid inter-agency transition system are most apparent in students' frequent inter-setting transitions between nontraditional and home schools.

No Wasted Moments: Planning Purposeful Transitions

ERIC Educational Resources Information Center

Nicolucci, Sandra

2010-01-01

This article focuses on the nature of the "transitional minutes" in "any" music class. When transitional minutes before, during, and after rehearsals and classes are unplanned and left to chance, much viable and valuable teaching time is lost. When transitional minutes are well structured, learning can proceed efficiently. One…

Steady-state and time-resolved studies on the photophysical properties of fullerene-pyropheophorbide a complexes in polar and nonpolar solvents

NASA Astrophysics Data System (ADS)

Ermilov, E. A.; Al-Omari, S.; Helmreich, M.; Jux, N.; Hirsch, A.; Röder, B.

2004-04-01

A novel monofullerene-bis(pyropheophorbide a) dyad has been photophysically characterized by steady-state as well as time-resolved techniques. It was revealed that in this complex strong and fast quenching of the first excited singlet state of the pyropheophorbide a (pyroPheo) molecule occurs by efficient photoinduced electron transfer to the fullerene moiety in both polar (DMF) and nonpolar (toluene) solvents. In DMF the energy of the charge-separated state is 0.94 eV and it undergoes directly transition to the ground state resulting in a very low value of photosensitized singlet oxygen generation. In contrast to the situation in a polar solvent, in toluene the charge-separated state lies above the exited triplet state of pyroPheo as well as that of C 60. It has been shown that in a nonpolar solvent a sufficient amount of singlet oxygen was generated by energy transfer from the excited triplet state of pyroPheo which has been populated via relaxation of the charge-separated state.

Folding of a LysM Domain: Entropy-Enthalpy Compensation in the Transition State of an Ideal Two-state Folder

PubMed Central

Nickson, Adrian A.; Stoll, Kate E.; Clarke, Jane

2008-01-01

Protein-engineering methods (Φ-values) were used to investigate the folding transition state of a lysin motif (LysM) domain from Escherichia coli membrane-bound lytic murein transglycosylase D. This domain consists of just 48 structured residues in a symmetrical βααβ arrangement and is the smallest αβ protein yet investigated using these methods. An extensive mutational analysis revealed a highly robust folding pathway with no detectable transition state plasticity, indicating that LysM is an example of an ideal two-state folder. The pattern of Φ-values denotes a highly polarised transition state, with significant formation of the helices but no structure within the β-sheet. Remarkably, this transition state remains polarised after circularisation of the domain, and exhibits an identical Φ-value pattern; however, the interactions within the transition state are uniformly weaker in the circular variant. This observation is supported by results from an Eyring analysis of the folding rates of the two proteins. We propose that the folding pathway of LysM is dominated by enthalpic rather than entropic considerations, and suggest that the lower entropy cost of formation of the circular transition state is balanced, to some extent, by the lower enthalpy of contacts within this structure. PMID:18538343

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

PubMed

Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

2014-08-14

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

Light signaling controls nuclear architecture reorganization during seedling establishment

PubMed Central

Bourbousse, Clara; Mestiri, Imen; Zabulon, Gerald; Bourge, Mickaël; Formiggini, Fabio; Koini, Maria A.; Brown, Spencer C.; Fransz, Paul; Bowler, Chris; Barneche, Fredy

2015-01-01

The spatial organization of chromatin can be subject to extensive remodeling in plant somatic cells in response to developmental and environmental signals. However, the mechanisms controlling these dynamic changes and their functional impact on nuclear activity are poorly understood. Here, we determined that light perception triggers a switch between two different nuclear architectural schemes during Arabidopsis postembryonic development. Whereas progressive nucleus expansion and heterochromatin rearrangements in cotyledon cells are achieved similarly under light and dark conditions during germination, the later steps that lead to mature nuclear phenotypes are intimately associated with the photomorphogenic transition in an organ-specific manner. The light signaling integrators DE-ETIOLATED 1 and CONSTITUTIVE PHOTOMORPHOGENIC 1 maintain heterochromatin in a decondensed state in etiolated cotyledons. In contrast, under light conditions cryptochrome-mediated photoperception releases nuclear expansion and heterochromatin compaction within conspicuous chromocenters. For all tested loci, chromatin condensation during photomorphogenesis does not detectably rely on DNA methylation-based processes. Notwithstanding, the efficiency of transcriptional gene silencing may be impacted during the transition, as based on the reactivation of transposable element-driven reporter genes. Finally, we report that global engagement of RNA polymerase II in transcription is highly increased under light conditions, suggesting that cotyledon photomorphogenesis involves a transition from globally quiescent to more active transcriptional states. Given these findings, we propose that light-triggered changes in nuclear architecture underlie interplays between heterochromatin reorganization and transcriptional reprogramming associated with the establishment of photosynthesis. PMID:25964332

Dynamic Textures Modeling via Joint Video Dictionary Learning.

PubMed

Wei, Xian; Li, Yuanxiang; Shen, Hao; Chen, Fang; Kleinsteuber, Martin; Wang, Zhongfeng

2017-04-06

Video representation is an important and challenging task in the computer vision community. In this paper, we consider the problem of modeling and classifying video sequences of dynamic scenes which could be modeled in a dynamic textures (DT) framework. At first, we assume that image frames of a moving scene can be modeled as a Markov random process. We propose a sparse coding framework, named joint video dictionary learning (JVDL), to model a video adaptively. By treating the sparse coefficients of image frames over a learned dictionary as the underlying "states", we learn an efficient and robust linear transition matrix between two adjacent frames of sparse events in time series. Hence, a dynamic scene sequence is represented by an appropriate transition matrix associated with a dictionary. In order to ensure the stability of JVDL, we impose several constraints on such transition matrix and dictionary. The developed framework is able to capture the dynamics of a moving scene by exploring both sparse properties and the temporal correlations of consecutive video frames. Moreover, such learned JVDL parameters can be used for various DT applications, such as DT synthesis and recognition. Experimental results demonstrate the strong competitiveness of the proposed JVDL approach in comparison with state-of-the-art video representation methods. Especially, it performs significantly better in dealing with DT synthesis and recognition on heavily corrupted data.

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields.

PubMed

Klinkusch, Stefan; Tremblay, Jean Christophe

2016-05-14

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.

SIMULATION FROM ENDPOINT-CONDITIONED, CONTINUOUS-TIME MARKOV CHAINS ON A FINITE STATE SPACE, WITH APPLICATIONS TO MOLECULAR EVOLUTION.

PubMed

Hobolth, Asger; Stone, Eric A

2009-09-01

Analyses of serially-sampled data often begin with the assumption that the observations represent discrete samples from a latent continuous-time stochastic process. The continuous-time Markov chain (CTMC) is one such generative model whose popularity extends to a variety of disciplines ranging from computational finance to human genetics and genomics. A common theme among these diverse applications is the need to simulate sample paths of a CTMC conditional on realized data that is discretely observed. Here we present a general solution to this sampling problem when the CTMC is defined on a discrete and finite state space. Specifically, we consider the generation of sample paths, including intermediate states and times of transition, from a CTMC whose beginning and ending states are known across a time interval of length T. We first unify the literature through a discussion of the three predominant approaches: (1) modified rejection sampling, (2) direct sampling, and (3) uniformization. We then give analytical results for the complexity and efficiency of each method in terms of the instantaneous transition rate matrix Q of the CTMC, its beginning and ending states, and the length of sampling time T. In doing so, we show that no method dominates the others across all model specifications, and we give explicit proof of which method prevails for any given Q, T, and endpoints. Finally, we introduce and compare three applications of CTMCs to demonstrate the pitfalls of choosing an inefficient sampler.

Resolution-of-identity stochastic time-dependent configuration interaction for dissipative electron dynamics in strong fields

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

Klinkusch, Stefan; Tremblay, Jean Christophe

In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electronmore » ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.« less

SparseMaps—A systematic infrastructure for reduced-scaling electronic structure methods. III. Linear-scaling multireference domain-based pair natural orbital N-electron valence perturbation theory

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

Guo, Yang; Sivalingam, Kantharuban; Neese, Frank, E-mail: Frank.Neese@cec.mpg.de

2016-03-07

Multi-reference (MR) electronic structure methods, such as MR configuration interaction or MR perturbation theory, can provide reliable energies and properties for many molecular phenomena like bond breaking, excited states, transition states or magnetic properties of transition metal complexes and clusters. However, owing to their inherent complexity, most MR methods are still too computationally expensive for large systems. Therefore the development of more computationally attractive MR approaches is necessary to enable routine application for large-scale chemical systems. Among the state-of-the-art MR methods, second-order N-electron valence state perturbation theory (NEVPT2) is an efficient, size-consistent, and intruder-state-free method. However, there are still twomore » important bottlenecks in practical applications of NEVPT2 to large systems: (a) the high computational cost of NEVPT2 for large molecules, even with moderate active spaces and (b) the prohibitive cost for treating large active spaces. In this work, we address problem (a) by developing a linear scaling “partially contracted” NEVPT2 method. This development uses the idea of domain-based local pair natural orbitals (DLPNOs) to form a highly efficient algorithm. As shown previously in the framework of single-reference methods, the DLPNO concept leads to an enormous reduction in computational effort while at the same time providing high accuracy (approaching 99.9% of the correlation energy), robustness, and black-box character. In the DLPNO approach, the virtual space is spanned by pair natural orbitals that are expanded in terms of projected atomic orbitals in large orbital domains, while the inactive space is spanned by localized orbitals. The active orbitals are left untouched. Our implementation features a highly efficient “electron pair prescreening” that skips the negligible inactive pairs. The surviving pairs are treated using the partially contracted NEVPT2 formalism. A detailed comparison between the partial and strong contraction schemes is made, with conclusions that discourage the strong contraction scheme as a basis for local correlation methods due to its non-invariance with respect to rotations in the inactive and external subspaces. A minimal set of conservatively chosen truncation thresholds controls the accuracy of the method. With the default thresholds, about 99.9% of the canonical partially contracted NEVPT2 correlation energy is recovered while the crossover of the computational cost with the already very efficient canonical method occurs reasonably early; in linear chain type compounds at a chain length of around 80 atoms. Calculations are reported for systems with more than 300 atoms and 5400 basis functions.« less

14 CFR 375.50 - Transit flights; scheduled international air service operations.

Code of Federal Regulations, 2010 CFR

2010-01-01

... WITHIN THE UNITED STATES Transit Flights § 375.50 Transit flights; scheduled international air service operations. (a) Requirement of notice. Scheduled international air services proposed to be operated pursuant to the International Air Services Transit Agreement in transit across the United States may not be...

14 CFR 375.50 - Transit flights; scheduled international air service operations.

Code of Federal Regulations, 2011 CFR

2011-01-01

... WITHIN THE UNITED STATES Transit Flights § 375.50 Transit flights; scheduled international air service operations. (a) Requirement of notice. Scheduled international air services proposed to be operated pursuant to the International Air Services Transit Agreement in transit across the United States may not be...

14 CFR 375.50 - Transit flights; scheduled international air service operations.

Code of Federal Regulations, 2014 CFR

2014-01-01

... WITHIN THE UNITED STATES Transit Flights § 375.50 Transit flights; scheduled international air service operations. (a) Requirement of notice. Scheduled international air services proposed to be operated pursuant to the International Air Services Transit Agreement in transit across the United States may not be...

14 CFR 375.50 - Transit flights; scheduled international air service operations.

Code of Federal Regulations, 2013 CFR

2013-01-01

... WITHIN THE UNITED STATES Transit Flights § 375.50 Transit flights; scheduled international air service operations. (a) Requirement of notice. Scheduled international air services proposed to be operated pursuant to the International Air Services Transit Agreement in transit across the United States may not be...

14 CFR 375.50 - Transit flights; scheduled international air service operations.

Code of Federal Regulations, 2012 CFR

2012-01-01

... WITHIN THE UNITED STATES Transit Flights § 375.50 Transit flights; scheduled international air service operations. (a) Requirement of notice. Scheduled international air services proposed to be operated pursuant to the International Air Services Transit Agreement in transit across the United States may not be...

Molecular Chirality: Enantiomer Differentiation by High-Resolution Spectroscopy

NASA Astrophysics Data System (ADS)

Hirota, Eizi

2014-06-01

I have demonstrated that triple resonance performed on a three-rotational-level system of a chiral molecule of C1 symmetry exhibits signals opposite in phase for different enantiomers, thereby making enantiomer differentiation possible by microwave spectroscopy This prediction was realized by Patterson et al. on 1,2-propanediol and 1,3-butanediol. We thus now add a powerful method: microwave spectroscopy to the study of chiral molecules, for which hitherto only the measurement of optical rotation has been employed. Although microwave spectroscopy is applied to molecules in the gaseous phase, it is unprecedentedly superior to the traditional method: polarimeter in resolution, accuracy, sensitivity, and so on, and I anticipate a new fascinating research area to be opened in the field of molecular chirality. More versatile and efficient systems should be invented and developed for microwave spectroscopy, in order to cope well with new applications expected for this method For C2 and Cn (n ≥ 3)chiral molecules, the three-rotational-level systems treated above for C1 molecules are no more available within one vibronic state. It should, however, be pointed out that, if we take into account an excited vibronic state in addition to the ground state, for example, we may encounter many three-level systems. Namely, either one rotational transition in the ground state is combined with two vibronic transitions, or such a rotational transition in an excited state may be connected through two vibronic transitions to a rotational level in the ground state manifold. The racemization obviously plays a crucial role in the study of molecular chirality. However, like many other terms employed in chemistry, this important process has been "defined" only in a vague way, in other words, it includes many kinds of processes, which are not well classified on a molecular basis. I shall mention an attempt to obviate these shortcomings in the definition of racemization and also to clarify the implicit assumptions made in Hund's paradox. E. Hirota, 3rd Molecular Science Symposium, Nagoya, September 2009, E. Hirota, Proc. Jpn. Acad. Ser. B, 88, 120 (2012). D. Patterson, M. Schnell and J. M. Doyle, Nature 497, 475 (2013), D. Patterson and J. M. Doyle, Phys. Rev. Lett. 111, 023008 (2013). F. Hund, Z. Phys. 43, 805 (1927).

Exploring the Connection Between Sampling Problems in Bayesian Inference and Statistical Mechanics

NASA Technical Reports Server (NTRS)

Pohorille, Andrew

2006-01-01

The Bayesian and statistical mechanical communities often share the same objective in their work - estimating and integrating probability distribution functions (pdfs) describing stochastic systems, models or processes. Frequently, these pdfs are complex functions of random variables exhibiting multiple, well separated local minima. Conventional strategies for sampling such pdfs are inefficient, sometimes leading to an apparent non-ergodic behavior. Several recently developed techniques for handling this problem have been successfully applied in statistical mechanics. In the multicanonical and Wang-Landau Monte Carlo (MC) methods, the correct pdfs are recovered from uniform sampling of the parameter space by iteratively establishing proper weighting factors connecting these distributions. Trivial generalizations allow for sampling from any chosen pdf. The closely related transition matrix method relies on estimating transition probabilities between different states. All these methods proved to generate estimates of pdfs with high statistical accuracy. In another MC technique, parallel tempering, several random walks, each corresponding to a different value of a parameter (e.g. "temperature"), are generated and occasionally exchanged using the Metropolis criterion. This method can be considered as a statistically correct version of simulated annealing. An alternative approach is to represent the set of independent variables as a Hamiltonian system. Considerab!e progress has been made in understanding how to ensure that the system obeys the equipartition theorem or, equivalently, that coupling between the variables is correctly described. Then a host of techniques developed for dynamical systems can be used. Among them, probably the most powerful is the Adaptive Biasing Force method, in which thermodynamic integration and biased sampling are combined to yield very efficient estimates of pdfs. The third class of methods deals with transitions between states described by rate constants. These problems are isomorphic with chemical kinetics problems. Recently, several efficient techniques for this purpose have been developed based on the approach originally proposed by Gillespie. Although the utility of the techniques mentioned above for Bayesian problems has not been determined, further research along these lines is warranted

Polarization-dependent Rabi oscillations in single InGaAs quantum dots

NASA Astrophysics Data System (ADS)

Besombes, L.; Baumberg, J. J.; Motohisa, J.

2004-04-01

Measurements of optical Rabi oscillations in the excited states of individual InGaAs are presented. Under pulsed resonant excitation we observe Rabi oscillations with increasing pulse area, which are damped after the first maximum and minimum. We show that the observed damping comes from an additional non-resonant generation of carriers in the quantum dot. The observation of Rabi oscillations provides an efficient way of directly measuring the excitonic transitions' dipole moments. A polarization anisotropy of the dipole moment is resolved in some of the quantum dots.

A technology mapping based on graph of excitations and outputs for finite state machines

NASA Astrophysics Data System (ADS)

Kania, Dariusz; Kulisz, Józef

2017-11-01

A new, efficient technology mapping method of FSMs, dedicated for PAL-based PLDs is proposed. The essence of the method consists in searching for the minimal set of PAL-based logic blocks that cover a set of multiple-output implicants describing the transition and output functions of an FSM. The method is based on a new concept of graph: the Graph of Excitations and Outputs. The proposed algorithm was tested using the FSM benchmarks. The obtained results were compared with the classical technology mapping of FSM.

The analytical approach to optimization of active region structure of quantum dot laser

NASA Astrophysics Data System (ADS)

Korenev, V. V.; Savelyev, A. V.; Zhukov, A. E.; Omelchenko, A. V.; Maximov, M. V.

2014-10-01

Using the analytical approach introduced in our previous papers we analyse the possibilities of optimization of size and structure of active region of semiconductor quantum dot lasers emitting via ground-state optical transitions. It is shown that there are optimal length' dispersion and number of QD layers in laser active region which allow one to obtain lasing spectrum of a given width at minimum injection current. Laser efficiency corresponding to the injection current optimized by the cavity length is practically equal to its maximum value.

Study of intermediates from transition metal excited-state electron-transfer reactions

NASA Astrophysics Data System (ADS)

Hoffman, M. Z.

1984-03-01

Attention during the past year focused on MV(+)., the reduced methyl viologen radical cation, which is a precursor to the formation of H2 in the photosensitized reduction of water. Through the use of photochemical and radiation chemical techniques, the efficiency of interaction of MV(+). with colloidal Pt, the stability of MV(+). as a function of pH, the quantum yield of formation of MV(+). in the Ru(bpy)3(2+)/MV(2+)/EDTA system, and the formation of photoactive charge-transfer complexes between MV(2+) and sacrificial electron donors were studied.

Microwave-Based Reaction Screening: Tandem Retro-Diels-Alder/Diels-Alder Cycloadditions of ortho-Quinol Dimers

PubMed Central

Dong, Suwei; Cahill, Kath arine J.; Kang, Moon -Il; Colburn, Nancy H.; Henrich, Curtis J.; Wilson, Jennifer A.; Beutler, John A.; Johnson, Richard P.; Porco, John A.

2011-01-01

We have accomplished a parallel screen of cycloaddition partners for ortho-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of ortho-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of ortho-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor. PMID:21942286

An abstract approach to evaporation models in rarefied gas dynamics

NASA Astrophysics Data System (ADS)

Greenberg, W.; van der Mee, C. V. M.

1984-03-01

Strong evaporation models involving 1D stationary problems with linear self-adjoint collision operators and solutions in abstract Hilbert spaces are investigated analytically. An efficient algorithm for locating the transition from existence to nonexistence of solutions is developed and applied to the 1D and 3D BGK model equations and the 3D BGK model in moment form, demonstrating the nonexistence of stationary evaporation states with supersonic drift velocities. Applications to similar models in electron and phonon transport, radiative transfer, and neutron transport are suggested.

Future US energy demands based upon traditional consumption patterns lead to requirements which significantly exceed domestic supply

NASA Technical Reports Server (NTRS)

1975-01-01

Energy consumption in the United States has risen in response to both increasing population and to increasing levels of affluence. Depletion of domestic energy reserves requires consumption modulation, production of fossil fuels, more efficient conversion techniques, and large scale transitions to non-fossile fuel energy sources. Widening disparity between the wealthy and poor nations of the world contributes to trends that increase the likelihood of group action by the lesser developed countries to achieve political and economic goals. The formation of anticartel cartels is envisioned.

Electron Correlation and Tranport Properties in Nuclear Fuel Materials

NASA Astrophysics Data System (ADS)

Yin, Quan; Haule, Kristjan; Kotliar, Gabriel; Savrasov, Sergey; Pickett, Warren

2011-03-01

Using first principle LDA+DMFT method, we conduct a systematic study on the correlated electronic structures and transport properties of select actinide carbides, nitrides, and oxides, many of which are nuclear fuel materials. Our results capture the metal--insulator Mott transition within the studied systems, and the appearance of the Zhang-Rice state in uranium dioxide. More importantly, by understanding the physics underlying their transport properties, we suggest ways to improve the efficiency of currently used fuels. This work is supported by the DOE Nuclear Energy University Program, contract No. 00088708.