Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “H”

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.

At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Probing High-Temperature Amine Chemistry: Is the Reaction NH 3 + NH 2 ⇌ N 2 H 3 + H 2 Important?

The reaction NH 3 + NH 2 ⇌ N 2 H 3 + H 2 (R1) has been identified as a key step to explain experimental results for pyrolysis and oxidation of ammonia. However, no direct experimental or theoretical evidence for the reaction has been reported. In the present work, the reaction was studied by ab initio theory and by reinterpretation of experimental data. We could not locate a transition state for R1 occurring as a direct process, but alternative mechanisms yielded an upper bound to k 1 of 1.5 × 10 13 exp(–58.9 kcal mol –1 /RT) cm 3 mol –1 s –1 over 1000–2500 K, several orders of magnitude lower than values applied in modeling. Consistent with the theoretical work, re-evaluation of NH 3 pyrolysis data supported a very low value of k 1 . However, this finding opens up a novel unresolved issue. Current kinetic models cannot capture the NH 3 oxidation behavior in a number of laminar flow reactor and jet-stirred reactor experiments without adopting an improbably high value for k 1 . Furthermore, important oxidation steps might be underestimated or missing from mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Computational Screening of Supported Metal Oxide Nanoclusters for Methane Activation: Insights into Homolytic versus Heterolytic C–H Bond Dissociation

Since its discovery in zeolites, the [CuOCu] 2+ motif has played an important role in our understanding of selective methane activation over supported metal oxide nanoclusters. Although there are two known C-H bond dissoci-ation mechanisms, namely homolytic and heterolytic cleavage, most computational studies on optimizing metal oxide nanoclusters for improved methane activation reactivity have focused only on the homolytic mechanism. In this work, both mechanisms were examined for a set of 21 mixed metal oxide complexes of the form of [M 1 OM 2 ] 2+ (M 1 , M 2 = Mn, Fe, Co, Ni, Cu, Zn). Except for pure copper, heterolytic cleavage was found to be the dominant C-H bond activation pathway for all systems. Furthermore, mixed systems including [CuOMn] 2+ , [CuONi] 2+ , and [CuOZn] 2+ are predicted to possess similar methane activation activity as pure [CuOCu] 2+ . Furthermore, these results suggest that both homolytic and heterolytic mechanisms should be considered in computing methane activation energies on supported metal oxide nanoclusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Spin-Dependent Stereochemistry: A Nonadiabatic Quantum Dynamics Case Study of S + H 2 → SH + H Reaction

We study the spin-dependent stereodynamics of the S + H 2 → SH + H reaction by using full-dimensional quantum dynamics calculations with zero total nuclear angular momentum along the triplet 3 A" states and singlet 1 A' states. We find that the interplay between the electronic spin direction and the molecular geometry has a measurable influence on the singlet–triplet intersystem crossing reaction probabilities. Our results show that for some incident scattering angles in the body-fixed frame, the relative difference in intersystem crossing reaction probabilities (as determined between spin up and spin down initial states) can be as large as 15%. Furthermore, our findings are an ab initio demonstration of spin-dependent nonadiabatic dynamics, which we hope will shine light as far as understanding the chiral-induced spin selectivity effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The Hidden Path to the Resonance-Stabilized Fulvenallenyl Radical (C 7 H 5 ) via the Bimolecular Reaction of Tricarbon (C 3 , X 1 Σ g + ) with 1,3-Butadiene (C 4 H 6 ; X 1 A g )

Here, we report a novel bimolecular reaction pathway forming the resonance-stabilized fulvenallenyl radical (C 7 H 5 ) via the gas-phase reaction of tricarbon (C 3 , X 1 Σ g + ) with 1,3-butadiene (C 4 H 6 , X 1 A g ). Crossed molecular beam experiments combined with high-level electronic structures and statistical calculations reveal a rich potential energy surface. The reaction proceeds via tricarbon addition to a double bond of 1,3-butadiene, overcoming a 30 kJ mol –1 barrier, followed by ring closure, isomerizations (ring opening/closures, hydrogen shifts), and eventual hydrogen atom loss, yielding the fulvenallenyl radical (p1) almost exclusively via two dominant pathways. Considering the entrance barrier, this reaction may occur in high-temperature environments, like circumstellar envelopes of carbon stars, but is suppressed in colder regions such as molecular clouds and Titan’s atmosphere. These findings highlight the unexpected reactivity of small carbon clusters in shaping the molecular complexity of our universe, from the flicker of a flame to the death of a star.

Aromatic compounds↗
DOE OSTI2023

Observation of Slow Eigen-Zundel Interconversion in H + (H 2 O) 6 Clusters upon Isomer-Selective Vibrational Excitation and Buffer Gas Cooling in a Cryogenic Ion Trap

The formation of isomers when trapping floppy cluster ions in a temperature-controlled ion trap is a generally observed phenomenon. This involves collisional quenching of the ions initially formed at high temperature by buffer gas cooling until their internal energies fall below the barriers in the potential energy surface that separate them. Here we explore the kinetics at play in the case of the two isomers adopted by the H + (H 2 O) 6 cluster ion that differ in the proton accommodation motif. One of these is most like the Eigen cation with a tricoordinated hydronium motif (denoted E), and the other is most like the Zundel ion with the proton equally shared between two water molecules (denoted Z). After initial cooling to about 20 K in the radiofrequency (Paul) trap, the relative populations of these two spectroscopically distinct isomers are abruptly changed through isomer-selective photoexcitation of bands in the OH stretching region with a pulsed (~6 ns) infrared laser while the ions are in the trap. We then monitor the relaxation of the vibrationally excited clusters and reformation of the two cold isomers by recording infrared photodissociation spectra with a second IR laser as a function of delay time from the initial excitation. The latter spectra are obtained after ejecting the trapped ions into a time-of-flight photofragmentation mass spectrometer, thus enabling long (~0.1 s) delay times. Excitation of the Z isomer is observed to display long-lived vibrationally excited states that are collisionally cooled on a ms time scale, some of which quench into the E isomer. These excited E species then display spontaneous interconversion to the Z form on a ~10 ms time scale. Furthermore, these qualitative observations set the stage for a series of experimental measurements that can provide quantitative benchmarks for theoretical simulations of cluster dynamics and the potential energy surfaces that underlie them.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Energy barriers for Dy and H penetrating graphene on 6 H -SiC(0001) and freestanding bilayer graphene from first-principles calculations

Currently, intercalation of foreign guest atoms into two-dimensional (2D) layered van der Waals materials is an active research area motivated in part by the development of next-generation energy-storage technologies and optoelectronic devices. One such extensively studied 2D material is the graphene-on-SiC system. To realize and control the desired intercalated structures, it is fundamentally important to understand the kinetic process of intercalation. For the intercalation of a guest atom into graphene layers on SiC substrate, a critical kinetic parameter is the energy barrier of a guest atom penetrating the perfect graphene top layer into the gallery under it. However, accurate theoretical calculations for such penetration barriers are unavailable in literature. From our first-principles density functional theory calculations, we obtain the global energy barriers of 3.47 and 1.80 eV for single Dy and H atoms penetrating the graphene top layer on a graphene buffer layer supported by a Si-terminated 6H-SiC(0001) substrate, respectively. Furthermore, for comparison as well as for examining the lateral strain effects, we also obtain the global barriers of 5.05 and 1.50 eV for single Dy and H atoms penetrating freestanding bilayer graphene with a tensile strain of about 8.8% to match our model for supported graphene, as well as the global barriers of 7.21 and 4.18 eV for penetrating unstrained freestanding bilayer graphene, respectively. From corresponding minimum energy paths with multiple energy minima and saddle points, we can also obtain various local energy barriers and the global backward barrier from the graphene gallery back to the top surface.

2D materials↗
DOE OSTI2020

Direct functionalization of C-H bonds by electrophilic anions

Bond formation between two of the most inert molecules, alkanes and [B12X12]2- (X = Cl, Br), is performed in a two step process. Fragmentation of [B12X12]2- in the gas phase generates highly reactive [B12X11]- ions which spontaneously react with alkanes. The reaction mechanism was investigated using tandem mass spectrometry and gas-phase vibrational spectroscopy combined with electronic structure calculations. This effort revealed the unprecedented and counterintuitive electrophilic substitution of a proton in an alkane by a negatively charged ion resulting in a B-C bond formation. The product is a dianionic [B12X11CnH2n+1]2- species, in which H+ is electrostatically bound to the dianion. High flux ion soft-landing was performed to co-deposit [B12X11]- and complex organic molecules (phthalates) in thin layers on surfaces. Molecular structure analysis of the product films revealed that C-H functionalization by [B12X11]- occured in the presence of other more reactive functional groups. This observation demonstrates the utility of highly reactive fragment ions for defined bond formation processes and may pave the way to the use of gas phase ion chemistry for chemical synthesis in the condensed phase.

Warneke, Jonas↗
DOE OSTI2022

Expected ${\boldsymbol H \xrightarrow{} {\boldsymbol{\mu^+\mu^-}}} $ measurement precision with ${\boldsymbol { e^{+}e^{-}}{\bf \xrightarrow{}}{ \boldsymbol{Z(q\bar{q})H}}}$ production at the CEPC *

Here, a search for the dimuon decay of the Standard Model Higgs boson is performed using Monte Carlo simulated events to mimic data corresponding to an integrated luminosity of 5.6 ab -1 collected with the Circular Electron-Positron Collider detector in e + e - collisions at $\sqrt{s}$ =240 GeV. This study investigates the e + e - →ZH, Z → $q\bar{q}$, H → μ + μ - process, and the expected significance considering only the statistical uncertainty in the data for a background-only hypothesis for a Higgs boson with a mass of 125 GeV is found to be 6.1 σ, corresponding to a precision of 19%. The systematic impacts from the background Monte Carlo statistical fluctuations are estimated to be negligible. Moreover, the dependence of the measurement accuracy on the muon momentum resolution of the CEPC detector is investigated. It is found that the muon momentum resolution must be better than 204 MeV to discover the H →μμ process at the nominal integrated luminosity. If the resolution is 100% worse than the designed parameter, the integrated luminosity must be greater than 7.2 ab -1 to reach 5σ significance.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Generalized Korn’s inequalities for piecewise $H¹$ and $H²$ vector fields

The purpose of this paper is to construct a new class of discrete generalized Korn’s inequalities for piecewise $H^1$ vector fields and piecewise $H^2$ vector fields in three-dimensional space. The resulting Korn’s inequalities are different from the standard Korn’s inequalities, as they involve the trace-free symmetric gradient operator, in place of the usual symmetric gradient operator. Furthermore, it is anticipated that the new generalized Korn’s inequalities will be useful for the analysis of a broad range of finite element methods, including mixed finite element methods and discontinuous Galerkin methods.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Slow spin dynamics in the hyperhoneycomb lattice [ ( C 2 H 5 ) 3 NH ] 2 Cu 2 ( C 2 O 4 ) 3 revealed by H 1 NMR studies

We report the results of magnetic susceptibility χ and H 1 nuclear magnetic resonance (NMR) measurements on a three-dimensional hyperhoneycomb lattice compound [ ( C 2 H 5 ) 3 NH ] 2 Cu 2 ( C 2 O 4 ) 3 (CCCO). The average value of the antiferromagnetic (AFM) exchange coupling between the Cu 2 + ( S = 1 / 2 ) spins was determined to be J ~ 50 K from the χ measurements. No long-range magnetic ordering has been observed down to T = 50 mK, although NMR lines become slightly broader at low temperatures below 1 K. The broadening of the NMR spectrum observed below 1 K reveals that the Cu spin moments remain at this temperature, suggesting a non-spin-singlet ground state. The temperature and magnetic field dependence of 1 / T 1 at temperatures above 20 K is well explained by paramagnetic thermal spin fluctuations where the fluctuation frequency of Cu 2 + spins is higher than the NMR frequency of the order of megahertz. However, a clear signature of the slowing down of the Cu 2 + spin fluctuations was observed at low temperatures where 1 / T 1 shows a thermally activated behavior. The magnetic field dependence of the magnitude of the spin excitation gap suggests that the magnetic behaviors of CCCO are characterized as an AFM chain at low temperatures.

1-dimensional systems↗
DOE OSTI2020

Decentralized Control of Cascaded H-Bridge Inverters for Medium-Voltage Grid Integration: Preprint

This paper introduces a fully decentralized control strategy that allows for individualized active and reactive power control of H-bridge inverters connected in series. After formulating a model of the system power flows, we outline a communications-free approach where each inverter can act on independent commands. Inverter-level feedback is accomplished locally via a measurement of current flowing through the stack. A key feature is the lack of any centralized control routines or phase-locked loop. In this framework, the reactive power control loops achieve voltage synchronization among the converters and the grid, and the active power control loops modulate the terminal voltage amplitudes that influence power delivery. Furthermore, pole placement via state feedback is used to ensure stability of voltage synchronization while also enabling tracking of bidirectional power commands. Simulations are presented to validate the proposed approach.

communication-free modular converter control↗
DOE OSTI2021

Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

A complex role for chlorine radicals Radicals are atoms or molecules that are highly reactive because they have an unpaired electron. A common means of investigating whether they are involved in a particular reaction is to try to trap them with an acceptor compound. Yang et al. reinvestigated a photoinduced alkane oxidation reaction for which a trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed that chlorine, rather than alkoxy, was the key radical intermediate; the prior trapping results had stemmed from its complexation with alcohols. Science , abd8408, this issue p. 847

Science & Technology - Other Topics↗
DOE OSTI2021

Spectral Equivalence of Low-Order Discretizations for High-Order H(curl) and H(div) Spaces

In this paper, we present spectral equivalence results for high-order tensor product edge- and face-based finite elements for the H(curl) and H(div) function spaces. Specifically, we show for certain choices of shape functions that the mass and stiffness matrices of the high-order elements are spectrally equivalent to those for an assembly of low-order elements on the associated Gauss--Lobatto--Legendre mesh. Based on this equivalence, efficient preconditioners can be designed with favorable computational complexity. Numerical results are presented which confirm the theory and demonstrate the benefits of the equivalence results for overlapping Schwarz preconditioners.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Achieving 5,000-h and 8,000-h Low-PGM Electrode Durability on Automotive Drive Cycles

Whereas total Pt loading in anode and cathode catalysts below 0.125 mg cm −2 is required to meet the stringent cost target for automotive fuel cell systems (FCS) for light duty vehicles, low-loaded cathode catalysts are susceptible to unacceptable aging-related performance losses at high current densities. A framework model, validated by accelerated stress test data, has identified cell voltage, relative humidity (RH) and temperature as the key operating variables that affect degradation of a high-activity d-PtCo/C cathode catalyst with 0.1 mg cm −2 Pt loading. Drive cycle simulations indicate that these can be controlled by properly selecting the minimum FCS power, compressor-expander module (CEM) turndown, and stack coolant temperature. The optimum system parameters are 4-kW e minimum power for an 80-kW e FCS, CEM turndown of 12.5, and 66 °C average coolant exit temperature that combine to limit the maximum cell voltage to 850 mV and outlet RH to 90%–100%. Depending on Pt loading, the mismatch between actual and allowable degradation for 10% power loss over 5,000-h lifetime requires the stack to be oversized by 2.4%–5%, resulting in 8.4%–41% lower Pt utilization and 7.1%–20.5% penalty in stack cost. The corresponding results for 8,000-h lifetime are 10.3%-14% stack oversizing, 23%–51.8% lower Pt utilization, and 24.1%–35.4% stack cost penalty.

08 HYDROGEN↗
DOE OSTI2026

Raman spectroscopic investigation of ianthinite [U$_2^{4+}$(UO$_2$)$_4$O$_6$(OH)$_4$(H$_2$O)$_4$]·$5$H$_2$O, a rare mixed-valence uranium oxide hydrate

Ianthinite ([[U$_2^{4+}$(UO$_2$)$_4$O$_6$(OH)$_4$(H$_2$O)$_4$]·$5$H$_2$O) is an exotic mineral that possesses U in both tetravalent and hexavalent oxidation states and is structurally related to the U 3 O 8 polymorphs, which are commonly encountered technogenic materials in the nuclear fuel cycle. Despite the similarities between U 3 O 8 and ianthinite, and the importance of ianthinite in U paragenesis, no Raman spectra have been reported for this mineral. Here, to gain a more complete understanding of how structural attributes of ianthinite give rise to observable spectroscopic features and how these may relate to important materials in the nuclear fuel cycle, we provide, for the first time, Raman spectra of ianthinite. Ianthinite readily oxidizes at ambient conditions, complicating analysis of phase-pure material. Several analytical methods are employed herein to decouple the Raman features of ianthinite from its alteration product(s). First, a simple difference spectrum is presented, then results of Raman spectroscopic mapping are employed, and finally, we use a novel processing and analysis method. Each analysis method provides different insight into structural features that are unique to ianthinite, in particular, features that are attributable to U(IV) in distorted octahedral coordination in both ianthinite and U 3 O 8 phases.

Spano, Tyler L. [Oak Ridge National Laboratory (OR↗