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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 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Niki, Hiromi↗
DOE OSTI2026

Room-Temperature Methane Oxidation to Formaldehyde Mediated by CoMoO + Gas-Phase Cations

Formaldehyde (HCHO) is a fundamental chemical feedstock with widespread industrial applications. The direct oxidation of methane by oxygen to formaldehyde (CH 4 + 1/2O 2 → H 2 + HCHO) under mild conditions represents an attractive but challenging transformation, as it requires both activation of the inert C–H bonds of CH 4 and suppression of overoxidation to products such as carbon dioxide. In this work, mass spectrometry experiments combined with theoretical calculations reveal that CoMoO + cations can efficiently mediate this transformation at room temperature. The unique electronic structure of CoMoO + facilitates the formation of a crucial CoMoOCH 2 + intermediate during the reaction with CH 4 and prevents methanol formation. In the subsequent oxidation reaction, the Mo atom in CoMoO + serves as the active site for O 2 adsorption, and both Mo and Co atoms act as electron donors to activate O 2 , leading to the formation of the C–O bond in formaldehyde. This work reports the first gas-phase example of achieving conversion of CH 4 to HCHO and its radical derivatives by O 2 at room temperature using heteronuclear non-noble metal cations. Remarkably, the CoMoOCH 2 + cation maintains high reactivity after adsorbing one or two CH 4 molecules. Finally, these findings provide new mechanistic insights into selective methane activation and conversion.

aldehydes↗
DOE OSTI2016

NuGrid stellar data set. I. Stellar yields from H to BI for stars with metallicities Z = 0.02 and Z = 0.01

We provide a set of stellar evolution and nucleosynthesis calculations that applies established physics assumptions simultaneously to low- and intermediate-mass and massive star models. Our goal is to provide an internally consistent and comprehensive nuclear production and yield database for applications in areas such as presolar grain studies. Our non-rotating models assume convective boundary mixing (CBM) where it has been adopted before. We include 8 (12) initial masses for Z = 0.01 (0.02). Models are followed either until the end of the asymptotic giant branch phase or the end of Si burning, complemented by simple analytic core-collapse supernova (SN) models with two options for fallback and shock velocities. The explosions show which pre-SN yields will most strongly be effected by the explosive nucleosynthesis. We discuss how these two explosion parameters impact the light elements and the s and p process. For low- and intermediate-mass models, our stellar yields from H to Bi include the effect of CBM at the He-intershell boundaries and the stellar evolution feedback of the mixing process that produces the {sup 13}C pocket. All post-processing nucleosynthesis calculations use the same nuclear reaction rate network and nuclear physics input. We provide a discussion of the nuclear production across the entire mass range organized by element group. The entirety of our stellar nucleosynthesis profile and time evolution output are available electronically, and tools to explore the data on the NuGrid VOspace hosted by the Canadian Astronomical Data Centre are introduced.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

A planning study investigating dual-gated volumetric arc stereotactic treatment of primary renal cell carcinoma

This is a planning study investigating the dosimetric advantages of gated volumetric-modulated arc therapy (VMAT) to the end-exhale and end-inhale breathing phases for patients undergoing stereotactic treatment of primary renal cell carcinoma. VMAT plans were developed from the end-inhale (VMATinh) and the end-exhale (VMATexh) phases of the breathing cycle as well as a VMAT plan and 3-dimensional conformal radiation therapy plan based on an internal target volume (ITV) (VMATitv). An additional VMAT plan was created by giving the respective gated VMAT plan a 50% weighting and summing the inhale and exhale plans together to create a summed gated plan. Dose to organs at risk (OARs) as well as comparison of intermediate and low-dose conformity was evaluated. There was no difference in the volume of healthy tissue receiving the prescribed dose for the planned target volume (PTV) (CI100%) for all the VMAT plans; however, the mean volume of healthy tissue receiving 50% of the prescribed dose for the PTV (CI50%) values were 4.7 (± 0.2), 4.6 (± 0.2), and 4.7 (± 0.6) for the VMATitv, VMATinh, and VMATexh plans, respectively. The VMAT plans based on the exhale and inhale breathing phases showed a 4.8% and 2.4% reduction in dose to 30 cm{sup 3} of the small bowel, respectively, compared with that of the ITV-based VMAT plan. The summed gated VMAT plans showed a 6.2% reduction in dose to 30 cm{sup 3} of the small bowel compared with that of the VMAT plans based on the ITV. Additionally, when compared with the inhale and the exhale VMAT plans, a 4% and 1.5%, respectively, reduction was observed. Gating VMAT was able to reduce the amount of prescribed, intermediate, and integral dose to healthy tissue when compared with VMAT plans based on an ITV. When summing the inhale and exhale plans together, dose to healthy tissue and OARs was optimized. However, gating VMAT plans would take longer to treat and is a factor that needs to be considered.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2017

Assimilation of Wave Imaging Radar Observations for Real-time Wave-by-Wave Forecasting

This project addressed Topic 3: “Wave Measurement Instrumentation for Feed Forward Controls” under the FOA number DE-FOA-0000971. The overall goal of the program was to develop a phase-resolving wave forecasting technique for application to the active control of Wave Energy Conversion (WEC) devices. We have developed an approach that couples a wave imaging marine radar with a phase-resolving linear wave model for real-time wave field reconstruction and forward propagation of the wave field in space and time. The scope of the project was to develop and assess the performance of this novel forecasting system. Specific project goals were as follows: Develop and verify a fast, GPU-based (Graphical Processing Unit) wave propagation model suitable for phase-resolved computation of nearshore wave transformation over variable bathymetry; Compare the accuracy and speed of performance of the wave model against a deep water model in their ability to predict wave field transformation in the intermediate water depths (50 to 70 m) typical of planned WEC sites; Develop and implement a variational assimilation algorithm that can ingest wave imaging radar observations and estimate the time-varying wave conditions offshore of the domain of interest such that the observed wave field is best reconstructed throughout the domain and then use this to produce model forecasts for a given WEC location; Collect wave-resolving marine radar data, along with relevant in situ wave data, at a suitable wave energy test site, apply the algorithm to the field data, assess performance, and identify any necessary improvements; and Develop a production cost estimate that addresses the affordability of the wave forecasting technology and include in the Final Report. The developed forecasting algorithm (“Wavecast”) was evaluated for both speed and accuracy against a substantial synthetic dataset. Early in the project, performance tests definitively demonstrated that the system was capable of forecasting in real-time, as the GPU-based wave model backbone was very computationally efficient. The data assimilation algorithm was developed on a polar grid domain in order to match the sampling characteristics of the observation system (wave imaging marine radar). For verification purposes, a substantial set of synthetic wave data (i.e. forward runs of the wave model) were generated to be used as ground truth for comparison to the reconstructions and forecasts produced by Wavecast. For these synthetic cases, Wavecast demonstrated very good accuracy, for example, typical forecast correlation coefficients were between 0.84-0.95 when compared to the input data. Dependencies on shadowing, observational noise, and forecast horizon were also identified. During the second year of the project, a short field deployment was conducted in order to assess forecast accuracy under field conditions. For this, a radar was installed on a fishing vessel and observations were collected at the South Energy Test Site (SETS) off the coast of Newport, OR. At the SETS site, simultaneous in situ wave observations were also available owing to an ongoing field project funded separately. Unfortunately, the position and heading information that was available for the fishing vessel were not of sufficient accuracy in order to validate the forecast in a phase-resolving sense. Instead, a spectral comparison was made between the Wavecast forecast and the data from the in situ wave buoy. Although the wave and wind conditions during the field test were complex, the comparison showed a promising reconstruction of the wave spectral shape, where both peaks in the bimodal spectrum were represented. However, the total reconstructed spectral energy (across all directions and frequencies) was limited to 44% of the observed spectrum. Overall, wave-by-wave forecasting using a data assimilation approach based on wave imaging radar observations and a physics-based wave model shows promise for short-term phase-resolved predictions. Two recommendations for future work are as follows: first, we would recommend additional focused field campaigns for algorithm validation. The field campaign should be long enough to capture a range of wave conditions relevant to the target application and WEC site. In addition, it will be crucial to make sure the vessel of choice has high accuracy position and heading instrumentation (this instrumentation is commercially available but not standard on commercial fishing vessels). The second recommendation is to expand the model physics in the wave model backbone to include some nonlinear effects. Specifically, the third-order correction to the wave speed due to amplitude dispersion would be the next step in order to more accurately represent the phase speeds of large amplitude waves.

16 TIDAL AND WAVE POWER↗
DOE OSTI2016

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

Abstract. An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected) compared to daytime (average 0.9 µg m−3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 4.4 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. To our knowledge this is the first time that this has been shown when comparing VOC concentrations with SOA formation measured at the same time, rather than comparing measurements made at different times. Several recently developed instruments have quantified ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). An SOA yield of 18–58 % from those compounds can explain the observed SOA formation. S/IVOCs were the only pool of gas-phase carbon that was large enough to explain the observed SOA formation. This work suggests that these typically unmeasured gases play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. These measurements help clarify the magnitude of potential SOA formation from OH oxidation in forested environments and demonstrate methods for interpretation of ambient OFR measurements.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Auriga Streams – I: disrupting satellites surrounding Milky Way-mass haloes at multiple resolutions

In a hierarchically formed Universe, galaxies accrete smaller systems that tidally disrupt as they evolve in the host’s potential. We present a complete catalogue of disrupting galaxies accreted onto Milky Way-mass haloes from the Auriga suite of cosmological magnetohydrodynamic zoom-in simulations. We classify accretion events as intact satellites, stellar streams, or phase-mixed systems based on automated criteria calibrated to a visually classified sample, and match accretions to their counterparts in haloes re-simulated at higher resolution. Most satellites at the present day have lost substantial amounts of stellar mass – 67 per cent have $f_\text{bound} < 0.97$ (our threshold of lost stellar mass to no longer be considered intact), while 53 per cent satisfy a more stringent $f_\text{bound} < 0.8$. Streams typically outnumber intact systems, contribute a smaller fraction of overall accreted stars, and are substantial contributors at intermediate distances from the host centre ($\sim$0.1 to $\sim 0.7R_\text{200m}$, or $\sim$35 to $\sim$250 kpc for the Milky Way). We also identify accretion events that disrupt to form streams around massive intact satellites instead of the main host. Streams are more likely than intact or phase-mixed systems to have experienced pre-processing, suggesting this mechanism is important for setting disruption rates around Milky Way-mass haloes. All of these results are preserved across different simulation resolutions, though we do find some hints that satellites disrupt more readily at lower resolution. The Auriga haloes suggest that disrupting satellites surrounding Milky Way-mass galaxies are the norm and that a wealth of tidal features waits to be uncovered in upcoming surveys.

galaxies: haloes↗
DOE OSTI2022

Information transfer with a twist

Holographic duals for CFTs compactified on a Riemann surface Σ with a twist are cast in the language of wedge holography. Σ starts as part of the field theory geometry in the UV and becomes part of the internal space in the IR. This allows to associate entanglement entropies with splits of the internal space in the IR geometry. Decomposing the internal space in the IR and geometrizing the corresponding subsystems separately leads to two interacting gravitational systems, similar to the intermediate holographic description in braneworld models. For Σ = T 2 the setups are used to model information transfer from a black hole to a gravitating bath. This leads to Page curves with a phase structure which precisely mirrors that in braneworld models. The transition from geometric to non-geometric entropies is also discussed for Σ = S 2 as a model for more general internal spaces in AdS/CFT.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Predictive Dirac neutrino spectrum with strong CP solution in SU(5)L × SU(5)R unification

Abstract We develop a grand unified theory of matter and forces based on the gauge symmetry SU(5) L × SU(5) R with parity interchanging the two factor groups. Our main motivation for such a construction is to realize a minimal GUT embedding of left-right symmetric models that provide a parity solution to the strong CP problem without the axion. We show how the gauge couplings unify with an intermediate gauge symmetry SU(3) cL × SU(2) 2L × U(1) L × SU(5) R , and establish its consistency with proton decay constraints. The model correctly reproduces the observed fermion masses and mixings and leads tonaturally light Dirac neutrinoswith their Yukawa couplings suppressed by a factorM I /M G , the ratio of the intermediate scale to the GUT scale. We call this mechanism type II-Dirac seesaw. Furthermore, the model predictsδ CP = ±(130.4±1.2)° and$${m}_{{\nu }_{1}}$$= (4.8 – 8.4) meV for the Dirac CP phase and the lightest neutrino mass. We demonstrate how the model solves the strong CP problem via parity symmetry.

Physics↗
DOE OSTI2018

Coscattering/coannihilation dark matter in a fraternal twin Higgs model

Dark matter candidates arise naturally in many models that address the hierarchy problem. In the fraternal twin Higgs model which could explain the absence of the new physics signals at the Large Hadron Collider (LHC), there are several viable dark matter candidates. In this paper we study the twin neutrino in the mass range ~0.1-10 GeV as the dark matter. The thermal relic density is determined by the interplay of several annihilation and scattering processes between the twin neutrino, twin tau, and twin photon, depending on the order of the freeze-out temperatures of these processes. Besides the common coannihilation scenario where the relic density is controlled by the twin tau annihilation, it can realize the recently discovered coscattering phase if the scattering of the twin neutrino into the twin tau freezes out earlier than the twin tau annihilation. We also provide a method to calculate the thermal relic density in the intermediate regime where both coannihilation and coscattering processes contribute to the determination of the dark matter density. We show that the right amount of dark matter can be obtained in various scenarios in different regions of the parameter space. The current experimental constraints and future probes into the parameter space from direct detections, cosmological and astrophysical bounds, dark photon searches, and displaced decays at colliders, are discussed.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Converting polyisoprene rubbers into bio-jet fuels via a cascade hydropyrolysis and vapor-phase hydrogenation process

Producing alternative drop-in bio-jet fuels from biomass provides a promising approach to achieve carbon neutrality. Here, to upcycle biomass-based polyisoprene rubbers into jet-fuel range C 10 cycloalkane, we proposed a cascade hydropyrolysis and vapor-phase hydrogenation process in a flow-through two-stage pressurized fixed-bed reactor. The hydropyrolysis temperature in the first stage is of vital importance for the formation of primary limonene intermediate in the non-catalytic degradation of polyisoprene rubbers, and a reaction temperature of 460 °C maximized limonene yield to 588.6 mg/g for natural rubber and 546.2 mg/g for Eucommia rubber. Over a Pt/C catalyst loaded in the second stage, the limonene intermediate produced from the first-stage reactor can be completely hydrogenated, giving a 642.7 mg/g yield of jet-fuel range C 10 cycloalkane with 83.6% selectivity. The depolymerization mechanism of polyisoprene rubbers was thoroughly studied, and a competitive reaction between limonene hydrogenation and limonene dehydrogenation was observed. This is the first report on producing C 10 cycloalkane from natural rubbers via a cascade hydropyrolysis and hydrogenation process, providing a promising strategy to upcycle polyisoprene rubbers into bio-jet fuels.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Mechanochemistry-Induced Strong Metal–Support Interactions Construction toward Enhanced Hydrogenation

The construction of strong metal–support interactions (SMSIs) represented an attractive approach to producing supported noble metal nanocatalysts possessing enhanced stability by overlayer encapsulation. The development of facile approaches capable of achieving efficient, controllable, and extensive SMSI overlayer formation, particularly under neat and ambient conditions, is a long-standing challenge. In this work, a mechanochemistry-driven pathway was deployed for efficient and controllable SMSI construction under neat and ambient conditions to customize the capsulation degree and overlayer structures toward enhanced catalysis. The reducibility of the additives and the high interaction efficiency provided by the mechanochemical treatment could afford abundant active intermediates (e.g., Ti 3+ species and oxygen defects) within a short time to induce and tune the overlayer encapsulation. This facile approach could be extensively deployed to TiO2-derived nanocatalysts with diverse phases, diverse reducible metal oxides-involved systems, and different supported noble metal nanoparticles. Enhanced hydrogenation activity was achieved by the as-afforded nanocatalysts upon SMSI construction and further tuned by the encapsulation degree.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Epoxide Alcoholysis over M-BEA Zeolites: Effects of Alcohol Chain Length on Rates and Regioselectivities

The structures of nucleophilic reactants affect their coordination behavior among solvent molecules and kinetics of reactions with surface intermediates within the confines of fluidfilled pores of zeolites and other microporous materials. Consequently, rates and regioselectivities of diverse chemistries may depend sensitively on nucleophile identity in manners not observed for classic fluid phase reactions. Here, we examine the impact of varying the primary alcohol (ROH) chain length on the kinetics of 1,2-epoxybutane (C 4 H 8 O) ring-opening within Brønsted (Al-BEA) and Lewis acid (Zr-BEA) zeolites. Turnover rates increase by factors of ∼6 (Al-BEA) and 4-fold (Zr-BEA) between methanol and 1-hexanol, yet the reaction mechanisms remain comparable. Despite modest rate differences, apparent activation enthalpies calculated from rates and activities of solvated reactants decrease linearly by 12 (Al-BEA) to 33 kJ mol −1 (Zr- BEA) with increased proton affinity, which suggests bond formation energies for the nucleophile strongly influence rate increases. The molecular interpretation of these trends demonstrates, however, that the solvation of ring-opening transition states by zeolite pore structures and solvent molecules also governs rates. The impact of local solvating interactions appears most directly as changes in regioselectivities, which tend to enhance terminal alcohol formation with increasing ROH chain length. Regioselectivities largely do not vary with differences in fluid composition for a given ROH. The addition of H 2 O increases the number of hydrogen bonds among reactive species, and trends in regioselectivities imply that the decreased hydrogen bonding ability of longer chain ROH, and not the nucleophile strength or steric bulk, determines the regioselectivities of the resulting products. This work provides direct experimental evidence that nucleophilicity and hydrogen bonding influence reaction barriers and regioselectivities in zeolitecatalyzed epoxide ring-opening, offering pathways to better control reaction kinetics.

acidic zeolites↗
DOE OSTI2020

Regio- and Enantioselective Bromocyclization of Difluoroalkenes as a Strategy to Access Tetrasubstituted Difluoromethylene-Containing Stereocenters

Difluoromethylene-containing compounds have attracted substantial research interest over the past decades for their ability to mimic biological functions of traditional functional groups while providing a wide variety of pharmacological benefits bestowed by the C–F bond. Here, we report a novel strategy to access RCF 2 Br-containing heterocycles by regio- and enantioselective bromocyclization of difluoroalkenes enabled by chiral anion phase-transfer catalysis. The utility of this methodology was highlighted through a synthesis of an analogue of efavirenz, a drug used for treating HIV. Additionally, the synthetic versatility of the CF 2 Br intermediates was showcased through functionalization to a variety of enantioenriched α,α-difluoromethylene-containing products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Density Functional Theory Study of Oxygen Reduction Activity on Ultrathin Platinum Nanotubes

The structure, stability, and catalytic activity of a number of single- and double-wall platinum (n,m) nanotubes ranging in diameter from 0.3 to 2.0 nm were studied using plane-wave based density functional theory in the gas phase and water environment. The change in the catalytic activity toward the oxygen reduction reaction (ORR) with the size and chirality of the nanotube was studied by calculating equilibrium adsorption potentials for ORR intermediates and by constructing free energy diagrams in the ORR dissociative mechanism network. In addition, the stability of the platinum nanotubes is investigated in terms of electrochemical dissolution potentials and by determining the most stable state of the material as a function of pH and potential, as represented in Pourbaix diagrams. Our results show that the catalytic activity and the stability toward electrochemical dissolution depend greatly on the diameter and chirality of the nanotube. On the basis of the estimated overpotentials for ORR, we conclude that smaller, approximately 0.5 nm in diameter single-wall platinum nanotubes consistently show a huge, up to 400 mV larger overpotential than platinum, indicating very poor catalytic activity toward ORR. This is the result of substantial structural changes induced by the adsorption of any chemical species on these tubes. Single-wall n = m platinum nanotubes with a diameter larger than 1 nm have smaller ORR overpotentials than bulk platinum for up to 180 mV and thus show improved catalytic activity relative to bulk. We also predict that these nanotubes can endure the highest cell potentials but dissolution potentials are still for 110 mV lower than for the bulk, indicating a possible corrosion problem.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2024

Capturing the generation and structural transformations of molecular ions

Molecular ions are ubiquitous and play pivotal roles in many reactions, particularly in the context of atmospheric and interstellar chemistry. However, their structures and conformational transitions, particularly in the gas phase, are less explored than those of neutral molecules owing to experimental difficulties. A case in point is the halonium ions, whose highly reactive nature and ring strain make them short-lived intermediates that are readily attacked even by weak nucleophiles and thus challenging to isolate or capture before they undergo further reaction. Here we show that mega-electronvolt ultrafast electron diffraction (MeV-UED), used in conjunction with resonance-enhanced multiphoton ionization, can monitor the formation of 1,3-dibromopropane (DBP) cations and their subsequent structural dynamics forming a halonium ion. We find that the DBP + cation remains for a substantial duration of 3.6 ps in aptly named ‘dark states’ that are structurally indistinguishable from the DBP electronic ground state. The structural data, supported by surface-hopping simulations and ab initio calculations, reveal that the cation subsequently decays to iso-DBP + , an unusual intermediate with a four-membered ring containing a loosely bound bromine atom, and eventually loses the bromine atom and forms a bromonium ion with a three-membered-ring structure. We anticipate that the approach used here can also be applied to examine the structural dynamics of other molecular ions and thereby deepen our understanding of ion chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Probing two-field open inflation by resonant signals in correlation functions

We derive oscillatory signals in correlation functions in two-field open inflation by means of the in-in formalism; such signatures are caused by resonances between oscillations in the tunnelling field and fluctuations in the inflaton during the curvature dominated, intermediate and subsequent inflationary regime. While amplitudes are model-dependent, we find distinct oscillations in the power and bi-spectrum that can act as a direct probe of the curvature dominated phase and thus, indirectly, strengthen the claim of the string landscape if they were observed. We comment on the prospects of detecting these tell-tale signs in current experiments, which is challenging, but not impossible. At the technical level, we pay special attention to the applicability conditions for truncating fluctuations to the light (inflaton) field and derive upper limits on the oscillation amplitude of the heavy field. A violation of these bounds requires a multi-field analysis at the perturbed level.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

Orbital selective directional conductor in the two-orbital Hubbard model

Recently, we employed a developed many-body technique that allows for the incorporation of thermal effects, the rich phase diagram of a two-dimensional two-orbital (degenerate d xz and d yz ) Hubbard model is presented varying temperature and the repulsion U. The main result is the finding at intermediate U of an antiferromagnetic orbital selective state where an effective dimensional reduction renders one direction insulating and the other metallic. Possible realizations of this state are discussed. Additionally, we also study nematicity above the N eel temperature. After a careful finite-size scaling analysis, the nematicity temperature window appears to survive in the bulk limit, although it is very narrow.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗