SEARCH · Engineering Papers
Results for “C”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Design and validation of non-metal oxo complexes for C–H activation
Explore the source record for details and available documents.
Understanding improved electrochemical properties of NiO-doped NiF2–C composite conversion materials by X-ray absorption spectroscopy and pair distribution function analysis
Explore the source record for details and available documents.
On the role of the surface oxygen species during A–H (A = C, N, O) bond activation: a density functional theory study
Explore the source record for details and available documents.
Reaction dynamics of the 4-methylphenyl radical (C 6 H 4 CH 3 ; p-tolyl) with isoprene (C 5 H 8 ) – formation of dimethyldihydronaphthalenes
We probed the reaction of the 4-methylphenyl radical with isoprene under single collision conditions at a collision energy of 58 kJ mol -1 by exploiting the crossed molecular beam technique. Supported by the electronic structure calculations, the reaction was found to initially lead to a van-der-Waals complex without any barrier which can then isomerize by addition of the 4-methylphenyl radical to any one of the four carbon atoms of the 1,3-butadiene moiety of isoprene. The initial addition products isomerize with formal addition products preferentially to C1 and C4 carbon atoms of the isoprene. These structures further isomerize via hydrogen migration and cyclization; the reaction is terminated by a hydrogen atom elimination from the 4-methylphenyl moiety via tight exit transition states leading to two dimethyl-dihydronaphthalene isomers as the dominating products. Here, this study presents one of the very first bimolecular reactions of the 4-methylphenyl radical with unsaturated hydrocarbons and opens a path for the investigation of this reaction class in future experiments.
Formation of 5- and 6-methyl-1H-indene (C 10 H 10 ) via the reactions of the para-tolyl radical (C 6 H 4 CH 3 ) with allene (H 2 CCCH 2 ) and methylacetylene (HCCCH 3 ) under single collision conditions
The reactions of the p-tolyl radical with allene-d4 and methylacetylene-d4 as well as of the p-tolyl-d7 radical with methylacetylene-d1 and methylacetylene-d3 were carried out under single collision conditions at collision energies of 44–48 kJ mol -1 and combined with electronic structure and statistical (RRKM) calculations. Our experimental results indicated that the reactions of p-tolyl with allene-d4 and methylacetylene-d4 proceeded via indirect reaction dynamics with laboratory angular distributions spanning about 20° in the scattering plane. As a result, the center-of-mass translational energy distribution determined a reaction exoergicity of 149 ± 28 kJ mol -1 and exhibited a pronounced maximum at around 20 to 30 kJ mol -1 . In addition, the center-of-mass angular flux distribution T(θ) depicted a forward–backward symmetry and indicated geometric constraints upon the decomposing complex(es). Combining with calculations, these results propose that the bicyclic polycyclic aromatic hydrocarbons, 6-methyl-1H-indene (p1) and 5-methyl-1H-indene (p2), are formed under single collision conditions at fractions of at least 85% in both reaction systems. For the p-tolyl–methylacetylene system, experiments with partially deuterated reactants also reveal the formation of a third isomer p5 (1-methyl-4-(1-propynyl)benzene) at levels of 5–10%, highlighting the importance in conducting reactions with partially deuterated reactants to elucidate the underlying reaction pathways comprehensively.
Isolable iodosylarene and iodoxyarene adducts of Co and their O-atom transfer and C–H activation reactivity
We report an unusual series of discrete iodosyl- and iodoxyarene adducts of Co( ii ) including detailed studies of their O-transfer reactivity and mechanism.
Correction: Enhanced 5f-δ bonding in [U(C 7 H 7 ) 2 ] - : C K-edge XAS, magnetism, and ab initio calculations
The authors regret that two references to the multi-configurational pair-density functional theory methods used in the wavefunction calculations did not appear in the main article. The references were originally included in the Methods section of the Electronic Supplementary Information as ref. 17a and b, but should also have appeared in the second paragraph on page 9564. The references are listed below as ref. 1 and 2. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.
Reduction of (pddi)Cr reveals redox noninnocence via C–C bond formation amidst competing electrophilicity: [(cpta)CrMe n ] − ( n = 0, 1) and [(pta)Cr] −
Reversible cyclopropane formation is examined in a chromium diamide–diimine chelate complex via reduction. Sites of electrophilicity incur similar and divergent chemistry; structural, electrochemical, and calculational studies afford their rationale.
Direct observation of β-alkynyl eliminations from unstrained propargylic alkoxide Cu( i ) complexes by C–C bond cleavage
We report a comprehensive study on the synthesis, reactivity, mechanism, and computation for the β-alkynyl eliminations of secondary and tertiary propargylic alkoxides of Cu( i ) complexes supported by N-heterocyclic carbenes and diphosphines.
Four-electron oxidation and one-electron reduction of the bis(terphenylthiolate) U( II ) complex, U(SAr iPr6 ) 2 [Ar iPr6 = C 6 H 3 -2,6-(C 6 H 2 -2,4,6- i Pr 3 ) 2 ]
Here, the utility of the sterically bulky terphenylthiolate ligand, (SAr iPr6 ) 1− in expanding uranium reductive chemistry has been explored. Reduction of U(SAr iPr6 ) 2 I forms the U(II) complex, U(SAr iPr6 ) 2 , in which the metal is protected by the flanking arene rings of the ligand, but they move out of the way to accommodate the four electron reduction of PhN=NPh to form the U(VI) bis(imido) product U(SAr iPr6 ) 2 (=NPh) 2 (THF) 2 . Here, the KC 8 reduction of U(SAr iPr6 ) 2 generates a more reduced complex, KU(μ-SAr iPr6 ) 2 , initially identified by a −2.55 V vs. Fc + /Fc electrochemical reduction event in THF.
Taming Silylium Ions for Synthesis: N-Heterocycle Synthesis via Stereoselective C–C Bond Formation
Silylium ions (formally [R3Si]+) have long been the subject of investigations and significant debate in both theoretical and experimental chemistry, but few catalytic, synthetic applications have been reported due to the exceptionally high reactivity and Lewis acidity of these elusive species. Results to be discussed include the application of easily accessible silylium ion catalysts to the stereoselective synthesis of various N-heterocyclic pyrrolidine and piperidine scaffolds. The tested substrates are derived from the chiral pool and can be obtained in three high-yielding steps from amino alcohols; subsequent stereoselective silylium ion catalyzed Prins cyclization and trapping with R3Si–Nu nucleophiles (e.g., Nu = H, allyl, azide, and enol ethers) results in novel nitrogen-containing polycyclic scaffolds with potential medicinal chemistry applications.
Electron polarimetry at low energies in Hall C at JLab
Although the majority of Jefferson Lab experiments require multi-GeV electron beams, there have been a few opportunities to make electron beam polarization measurements at rather low energies. This proceedings will discuss some of the practical difficulties encountered in performing electron polarimetry via Mo/ller scattering at energies on the order of a few hundred MeV. Prospects for Compton polarimetry at very low energies will also be discussed. While Mo/ller scattering is likely the preferred method for electron polarimetry at energies below 500 MeV, there are certain aspects of the polarimeter and experiment design that must be carefully considered.
The graphene phonon dispersion with C{sup 12} and C{sup 13} isotopes
Using very uniform large scale chemical vapor deposition grown graphene transferred onto silicon, we were able to identify 15 distinct Raman lines associated with graphene monolayers. This was possible thanks to a combination of different carbon isotopes and different Raman laser energies and extensive averaging without increasing the laser power. This allowed us to obtain a detailed experimental phonon dispersion relation for many points in the Brillouin zone. We further identified a D+D' peak corresponding to a double phonon process involving both an inter- and intra-valley phonon. In order to both eliminate substrate effects and to probe large areas, we undertook to study Raman scattering for large scale chemical vapor deposition (CVD) grown graphene using two different isotopes (C12 and C13) so that we can effectively exclude and subtract the substrate contributions, since a heavier mass downshifts only the vibrational properties, while keeping all other properties the same.
Lithium diffusion at Si-C interfaces in silicon-graphene composites
Models of intercalated Li and its diffusion in Si-Graphene interfaces are investigated using density functional theory. Results suggest that the presence of interfaces alters the energetics of Li binding and diffusion significantly compared to bare Si or Graphene surfaces. Our results show that cavities along reconstructed Si surface provide diffusion paths for Li. Diffusion barriers calculated along these cavities are significantly lower than penetration barriers to bulk Si. Interaction with Si surface results in graphene defects, creating Li diffusion paths that are confined along the cavities but have still lower barrier than in bulk Si.
Water network-mediated, electron-induced proton transfer in [C{sub 5}H{sub 5}N ⋅ (H{sub 2}O){sub n}]{sup −} clusters
The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H{sub 2}O){sub n=3−5}]{sup −} clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH{sup (0)}, occupying one of the primary solvation sites of the OH{sup −}. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the “solvent coordinate” at the heart of a prototypical proton-coupled electron transfer reaction.