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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 1,171 records · Page 65
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Phenyl radical + propene: a prototypical reaction surface for aromatic-catalyzed 1,2-hydrogen-migration and subsequent resonance-stabilized radical formation

The C 9 H 11 potential energy surface (PES) was experimentally and theoretically explored because it is a relatively simple, prototypical alkylaromatic radical system. Although the C 9 H 11 PES has already been extensively studied both experimentally (under single-collision and thermal conditions) and theoretically, new insights were made in this work by taking a new experimental approach: flash photolysis combined with time-resolved molecular beam mass spectrometry (MBMS) and visible laser absorbance. The C 9 H 11 PES was experimentally accessed by photolytic generation of the phenyl radical and subsequent reaction with excess propene (C 6 H 5 + C 3 H 6 ). The overall kinetics of C 6 H 5 + C 3 H 6 was measured using laser absorbance with high time-resolution from 300 to 700 K and was found to be in agreement with earlier measurements over a lower temperature range. Five major product channels of C 6 H 5 + C 3 H 6 were observed with MBMS at 600 and 700 K, four of which were expected: hydrogen (H)-abstraction (measured by the stable benzene, C 6 H 6 , product), methyl radical (CH 3 )-loss (styrene detected), H-loss (phenylpropene isomers detected) and radical adduct stabilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ligand-triplet migration in iridium( iii ) cyclometalates featuring π-conjugated isocyanide ligands

The manipulation of the triplet excited state manifold leads to large differences in the photophysical properties within a given class of metal–organic chromophores. By the appropriate choice of ancillary ligand, large changes can be made both to the order and nature of the lowest excited states and therefore to the resulting photophysical properties. Herein, a series of four bis-2-phenylpyridine (ppy) cyclometalated Ir(III) compounds bearing two arylisocyanide ligands were synthesized and photophysically characterized to understand the effects of using ancillary ligands featuring systematic changes in π-conjugation. By varying the arylisocyanide ligands, the photoluminescence quantum yield ranged from 5% to 49% and the excited state lifetime ranged between 24 μs and 2 ms. These variations in photophysical response are consistent with lowering the triplet ligand-centered ( 3 LC) state of the arylisocyanide ligand as the π system was extended, confirmed by 77 K photoluminescence emission spectra and ultrafast transient absorption experiments. Here, the latter analysis gleaned detailed insight into the importance of the interplay of the 3 LC state of the phenylpyridine and arylisocyanide ligands in these polychromophic Ir(III) molecules.

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

Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator–metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atoms with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature T{sub j} is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature T{sub j}, the concentration of “free” holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3T{sub j}/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to T{sub j} hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (−1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p-type diamond with boron atom concentrations in the range from 3 × 10{sup 17} to 3 × 10{sup 20 }cm{sup −3}, i.e., up to the Mott transition. The model uses no fitting parameters.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Molecular dynamics simulation of the solid-liquid interface migration in terbium

In this work, we developed a Tb embedded atom method potential which properly reproduces the liquid structure obtained from the ab initio molecular dynamics simulation, the hexagonal close packed (hcp)-body-centered cubic (bcc) phase transformation, and melting temperatures. At least three crystal phases [hcp, face-centered cubic (fcc), and bcc] described by this potential can coexist with the liquid phase. Thus, the developed potential provides an excellent test bed for studies of the completive phase nucleation and growth in a single component system. The molecular dynamics simulation showed that all crystal phases can grow from the liquid phase close to their melting temperatures. However, in the cases of the hcp and fcc growth from the liquid phase at very large supercoolings, the bcc phase forms at the solid-liquid interface in the close packed orientations in spite of the fact that both hcp and fcc phases are more stable than the bcc phase at these temperatures. Finally, this bcc phase closes the hcp and fcc phase from the liquid such that the remaining liquid solidifies into the bcc phase. The initial hcp phase then slowly continues growing in expense of the bcc phase.

36 MATERIALS SCIENCE↗
DOE OSTI2018

The symmetrical quasi-classical approach to electronically nonadiabatic dynamics applied to ultrafast exciton migration processes in semiconducting polymers

In the last several years, a symmetrical quasi-classical (SQC) windowing model applied to the classical Meyer-Miller (MM) vibronic Hamiltonian has been shown to be a simple, efficient, general, and quite-accurate method for treating electronically nonadiabatic processes at the totally classical level. Here, the SQC/MM methodology is applied to ultrafast exciton dynamics in a Frenkel/site-exciton model of oligothiophene (OT) as a model of organic semiconductor polymers. In order to keep the electronic representation as compact and efficient as possible, the adiabatic version of the MM Hamiltonian was employed, with dynamical calculations carried out in the recently developed “kinematic momentum” representation, from which site/monomer-specific (diabatic) excitation probabilities were extracted using a new procedure developed in this work. The SQC/MM simulation results are seen to describe coherent exciton transport driven by planarization of a central torsion defect in the OT oligomer as well as to capture exciton self-trapping effects in good agreement with benchmark quantum calculations using the multi-layer multiconfiguration time-dependent Hartree approach. The SQC/MM calculations are also seen to significantly outperform the standard Ehrenfest approach, which shows serious discrepancies. Furthermore, these results are encouraging, not only because they illustrate a significant further application of the SQC/MM approach and its utility, but because they strongly suggest that classical mechanical simulations (with the potential for linear scaling efficiency) can be used to capture, quantitatively, important dynamical features of electronic excitation energy transfer in semiconducting polymers.

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

Isolation, Migration, and Local Recruitment Drive Persistence of Cutthroat Trout in Tributaries near American Falls Reservoir

Abstract We analyzed 67 SNPs to describe the genetics of Yellowstone Cutthroat Trout Oncorhynchus clarkii bouvieri in seven tributaries near American Falls Reservoir, Idaho. We detected Yellowstone Cutthroat Trout in all but one site despite significant historical stocking of Rainbow Trout O. mykiss. Three of four relatively low-elevation sites near the reservoir contained Yellowstone Cutthroat Trout in sympatry with early-generation hybrids and Rainbow Trout yet contained no physical barriers to admixture. A posteriori assignment tests suggested that migrants from a nearby headwater population in Ross Fork Creek and possibly recruitment by local-origin Yellowstone Cutthroat Trout with fluvial or adfluvial life histories drive persistence in these sites. In contrast, hybridization was rare or absent in headwater populations and was associated with complete or apparent physical isolation. We also compared genetic diversity of our samples with Yellowstone basin Yellowstone Cutthroat Trout and Bear River Bonneville Cutthroat Trout O. c. utah to examine possible historical gene flow resulting from hydrogeological connections during the Pleistocene. Multivariate analysis showed that most genetic variation among individuals was explained by divergence of Yellowstone basin Yellowstone Cutthroat Trout from our samples and Bear River Bonneville Cutthroat Trout, which supports recent mtDNA studies and a possible change in taxonomic nomenclature. Our results indicate that, due to relative isolation and downstream emigration, headwater populations are critical to the persistence of Yellowstone Cutthroat Trout and thus loss of such populations would likely threaten the subspecies throughout the region. Management actions to reduce threats from established, nonnative Rainbow Trout populations will likely have to be multifaceted and may include a combination of targeted removal of Rainbow Trout and hybrids and the use of physical barriers to prevent further dispersal. Received April 19, 2015; accepted February 7, 2016 Published online May 31, 2016

Bingham, Daniel M.↗