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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Dynamic crossover in deeply cooled water confined in MCM-41 at 4 kbar and its relation to the liquid-liquid transition hypothesis

With quasi-elastic neutron scattering, we study the single-particle dynamics of the water confined in a hydrophilic silica material, MCM-41, at 4 kbar. A dynamic crossover phenomenon is observed at 219 K. We compare this dynamic crossover with the one observed at ambient pressure and find that (a) above the crossover temperature, the temperature dependence of the characteristic relaxation time at ambient pressure exhibits a more evident super-Arrhenius behavior than that at 4 kbar. Especially, at temperatures below about 230 K, the relaxation time at 4 kbar is even smaller than that at ambient pressure. This feature is different from many other liquids. (b) Below the crossover temperature, the Arrhenius behavior found at ambient pressure has a larger activation energy compared to the one found at 4 kbar. We ascribe the former to the difference between the local structure of the low-density liquid (LDL) phase and that of the high-density liquid (HDL) phase, and the latter to the difference between the strength of the hydrogen bond of the LDL and that of the HDL. Therefore, we conclude that the phenomena observed in this paper are consistent with the LDL-to-HDL liquid-liquid transition hypothesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Mobility propagation and dynamic facilitation in superionic conductors

In an earlier work [V. A. Annamareddy et al., Phys. Rev. E 89, 010301(R) (2014)], we showed the manifestation of dynamical heterogeneity (DH)—the presence of clustered mobile and immobile regions—in UO{sub 2}, a model type II superionic conductor. In the current work, we demonstrate the mechanism of dynamic facilitation (DF) in two superionic conductors (CaF{sub 2} and UO{sub 2}) using atomistic simulations. Using the mobility transfer function, DF is shown to vary non-monotonically with temperature with the intensity of DF peaking at temperatures close to the superionic transition temperature (T{sub λ}). Both the metrics quantifying DH and DF show remarkable correspondence implying that DF, in the framework of kinematically constrained models, underpins the heterogeneous dynamics in type II superionic conductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Quantum dynamics on a three-sheeted six-dimensional ab initio potential-energy surface of the phosphine cation: Simulation of the photoelectron spectrum and the ultrafast radiationless decay dynamics

A diabatic three-sheeted six-dimensional potential-energy surface has been constructed for the ground state and the lowest excited state of the PH{sub 3}{sup +} cation. Coupling terms of Jahn-Teller and pseudo-Jahn-Teller origin up to eighth order had to be included to describe the pronounced anharmonicity of the surface due to multiple conical intersections. The parameters of the diabatic Hamiltonian have been optimized by fitting the eigenvalues of the potential-energy matrix to ab initio data calculated at the CASSCF/MRCI level employing the correlation-consistent triple-ζ basis. The theoretical photoelectron spectrum of phosphine and the non-adiabatic nuclear dynamics of the phosphine cation have been computed by propagating nuclear wave packets with the multiconfiguration time-dependent Hartree method. The theoretical photoelectron bands obtained by Fourier transformation of the autocorrelation function agree well with the experimental results. It is shown that the ultrafast non-radiative decay dynamics of the first excited state of PH{sub 3}{sup +} is dominated by the exceptionally strong Jahn-Teller coupling of the asymmetric bending vibrational mode together with a hyperline of conical intersections with the electronic ground state induced by the umbrella mode. Time-dependent population probabilities have been computed for the three adiabatic electronic states. The non-adiabatic Jahn-Teller dynamics within the excited state takes place within ≈5 fs. Almost 80% of the excited-state population decay to the ground state within about 10 fs. The wave packets become highly complex and delocalized after 20 fs and no further significant transfer of electronic population seems to occur up to 100 fs propagation time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

The structural phase diagram of uranyl fluoride (UO{sub 2}F{sub 2}), while incomplete, contains at least one anhydrous crystal structure and a second, zeolite-like structure with the formula [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} that can be produced by adding water to the anhydrous structure. While traditional diffraction measurements can easily differentiate these crystals, additional aqueous structures (in general of the form UO{sub 2}F{sub 2} + xH{sub 2}O) have been proposed as well. We present results using a novel sample environment setup to intercalate water during a quasielastic neutron scattering measurement over the course of 86 h. Our sample environment allows low-pressure (<2 atm) humid air flow across the sample coupled with a system to control the relative humidity of this air flow between 10% and 70%. The water dynamics in UO{sub 2}F{sub 2} and [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} are sufficiently different to distinguish them, with water in the latter executing a restricted diffusion (D = 2.7 × 10{sup −6} cm{sup 2}/s) within the structure's accessible pores (r = 3.17 Å) such that the dynamics can be used as a fingerprinting tool. We confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4}, and we demonstrate the feasibility of extending this approach to aqueous forms of UO{sub 2}F{sub 2} + xH{sub 2}O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

(Bi 0.2 Sb 0.8 ) 2 Te 3 based dynamic synapses with programmable spatio-temporal dynamics

Neuromorphic computing has recently emerged as a promising paradigm to overcome the von-Neumann bottleneck and enable orders of magnitude improvement in bandwidth and energy efficiency. However, existing complementary metal-oxide-semiconductor (CMOS) digital devices, the building block of our computing system, are fundamentally different from the analog synapses, the building block of the biological neural network—rendering the hardware implementation of the artificial neural networks (ANNs) not scalable in terms of area and power, with existing CMOS devices. In addition, the spatiotemporal dynamic, a crucial component for cognitive functions in the neural network, has been difficult to replicate with CMOS devices. Here, we present the first topological insulator (TI) based electrochemical synapse with programmable spatiotemporal dynamics, where long-term and short-term plasticity in the TI synapse are achieved through the charge transfer doping and ionic gating effects, respectively. We also demonstrate basic neuronal functions such as potentiation/depression and paired-pulse facilitation with high precision (>500 states per device), as well as a linear and symmetric weight update. We envision that the dynamic TI synapse, which shows promising scaling potential in terms of energy and speed, can lead to the hardware acceleration of truly neurorealistic ANNs with superior cognitive capabilities and excellent energy efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Improving dynamic collision frequencies: Impacts on dynamic structure factors and stopping powers in warm dense matter

Simulations and diagnostics of high-energy-density plasmas and warm dense matter rely on models of material response properties, both static and dynamic (frequency-dependent). Here, in this work, we systematically investigate variations in dynamic electron–ion collision frequencies ν(ω) in warm dense matter using data from a self-consistent-field average-atom model. We show that including the full quantum density of states, strong collisions, and inelastic collisions lead to significant changes in ν(ω). These changes result in red shifts and broadening of the plasmon peak in the dynamic structure factor, an effect observable in x-ray Thomson scattering spectra, and modify stopping powers around the Bragg peak. These changes improve the agreement of computationally efficient average-atom models with first-principles time-dependent density functional theory in warm dense aluminum, carbon, and deuterium.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Long-time atomistic dynamics through a new self-adaptive accelerated molecular dynamics method

A self-adaptive accelerated molecular dynamics method is developed to model infrequent atomic- scale events, especially those events that occur on a rugged free-energy surface. Key in the new development is the use of the total displacement of the system at a given temperature to construct a boost-potential, which is slowly increased to accelerate the dynamics. The temperature is slowly increased to accelerate the dynamics. By allowing the system to evolve from one steady-state con guration to another by overcoming the transition state, this self-evolving approach makes it possible to explore the coupled motion of species that migrate on vastly different time scales. The migrations of single vacancy (V) and small He-V clusters, and the growth of nano-sized He-V clusters in Fe for times in the order of seconds are studied by this new method. An interstitial- assisted mechanism is rst explored for the migration of a helium-rich He-V cluster, while a new two-component Ostwald ripening mechanism is suggested for He-V cluster growth.

Gao, N.↗
DOE OSTI2015

Resonance-mediated atomic ionization dynamics induced by ultraintense x-ray pulses

We describe the methodology of our recently developed Monte Carlo rate equation (MCRE) approach, which systematically incorporates bound-bound resonances to model multiphoton ionization dynamics induced by high-fluence, high-intensity x-ray free-electron laser (XFEL) pulses. These resonances are responsible for ionization far beyond that predicted by the sequential single photon absorption model and are central to a quantitative understanding of atomic ionization dynamics in XFEL pulses. We also present calculated multiphoton ionization dynamics for Kr and Xe atoms in XFEL pulses for a variety of conditions, to compare the effects of bandwidth, pulse duration, pulse fluence, and photon energy. This comprehensive computational investigation reveals areas in the photon energy–pulse fluence landscape where resonances are critically important. We also uncover a mechanism, preservation of inner-shell vacancies (PIVS), whereby radiation damage is enhanced at higher XFEL intensities and identify the sequence of core-outer–Rydberg, core-valence, and core-core resonances encountered during multiphoton x-ray ionization.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Asymptotic Dynamics of High Dynamic Range Stratified Turbulence

Direct numerical simulations of homogeneous sheared and stably stratified turbulence are considered to probe the asymptotic high-dynamic range regime suggested by Gargett et al. [1] and Shih et al. [2]. We consider statistically stationary configurations of the flow that span three decades in dynamic range defined by the separation between the Ozmidov length scale, L O = √ ε/N 3 , and the Kolmogorov length scale, L K = (ν 3 /ε) 1/4 , up to Re b ≡ (L O /L K ) 4/3 = ε/(νN 2 ) ~ O(1000), where ε is the mean turbulent kinetic energy dissipation rate, ν is the kinematic viscosity, and N is the buoyancy frequency. We isolate the effects of Reb, particularly on irreversible mixing, from the effects of other flow parameters of stratified and sheared turbulence [3]. Specifically, we evaluate the influence of dynamic range independent of initial conditions. We present evidence that the flow approaches an asymptotic state for Re b &#10886 300, characterized both by an asymptotic partitioning between the potential and kinetic energies and by the approach of components of the dissipation rate to their expected values under the assumption of isotropy. As Re b increases above 100, there is a slight decrease in the turbulent flux coefficient Γ = χ/ε, where χ is the dissipation rate of buoyancy variance, but, for this flow, there is no evidence of the commonly suggested Γ ∝ Re b -1/2 dependence when 100 ≤ Re b ≤ 1000.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Synchronization of Coupled Dynamical Systems: Tolerance to Weak Connectivity and Arbitrarily Bounded Time-Varying Delays

We study synchronization of coupled linear systems over networks with weak connectivity and time-varying delays. We focus on the case that the internal dynamics are time-varying but non-expansive. Both uniformly connected and infinitely connected communication topologies are considered. A new concept of P-synchronization is introduced and we first show that global asymptotic P-synchronization can be achieved over directed networks with uniform joint connectivity and arbitrarily bounded delays. We then study the case of the infinitely jointly connected communication topology. In particular, for the undirected communication topologies, it turns out that the existence of a uniform time interval for the communication topology is not necessary and P-synchronization can be achieved when the time varying delays are arbitrarily bounded. Simulations are given to validate the theoretical results.

Linear time-varying system, Synchronization, Switc↗