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All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Light Stau Phenomenology and the Higgs \gamma\gamma Rate

Recently, an excess of events consistent with a Higgs boson with mass of about 125 GeV was reported by the CMS and ATLAS experiments. This Higgs boson mass is consistent with the values that may be obtained in minimal supersymmetric extensions of the Standard Model (SM), with both stop masses less than a TeV and large mixing. The apparently enhanced photon production rate associated with this potential Higgs signal may be the result of light staus with large mixing. Large stau mixing and large coupling of the staus to the SM-like Higgs boson may be obtained for large values of tan {beta} and moderate to large values of the Higgsino mass parameter, {mu}. We study the phenomenological properties of this scenario, including precision electroweak data, the muon anomalous magnetic moment, Dark Matter, and the evolution of the soft supersymmetry-breaking parameters to high energies. We also analyze the possible collider signatures of light third generation sleptons and demonstrate that it is possible to find evidence of their production at the 8 TeV and the 14 TeV LHC. The most promising channel is stau and tau sneutrino associated production, with the sneutrino decaying into a W boson plus a light stau.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2017

Methodology and Software for Gross Defect Detection of Spent Nuclear Fuel at the Atucha-I Reactor [Novel Methodology and Software for Spent Fuel Gross Defect Detection at the Atucha-I Reactor]

Here, fuel assemblies in the spent fuel pool are stored by suspending them in two vertically stacked layers at the Atucha Unit 1 nuclear power plant (Atucha-I). This introduces the unique problem of verifying the presence of fuel in either layer without physically moving the fuel assemblies. Given that the facility uses both natural uranium and slightly enriched uranium at 0.85 wt% 235 U and has been in operation since 1974, a wide range of burnups and cooling times can exist in any given pool. A gross defect detection tool, the spent fuel neutron counter (SFNC), has been used at the site to verify the presence of fuel up to burnups of 8000 MWd/t. At higher discharge burnups, the existing signal processing software of the tool was found to fail due to nonlinearity of the source term with burnup.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Kinetic-energy dissipation and fluctuations in strongly damped heavy-ion collisions within the stochastic mean-field approach

Microscopic mean-field approaches have been successful in describing the most probable reaction outcomes in low-energy heavy-ion reactions. However, those approaches are known to severely underestimate dispersions of observables around the average values that has limited their applicability. Recently it has been shown that a quantal transport approach based on the stochastic mean-field (SMF) theory significantly improves the description, while its application has been limited so far to fragment mass and charge dispersions. In this work, we extend the quantal transport approach based on the SMF theory for relative kinetic energy dissipation and angular momentum transfer in low-energy heavy-ion reactions. Based on the SMF concept, analytical expressions are derived for the radial and tangential friction and associated diffusion coefficients. Those quantal transport coefficients are calculated microscopically in terms of single-particle orbitals within the time-dependent Hartree-Fock (TDHF) approach. As the first application of the proposed formalism, we consider the radial linear momentum dispersion, neglecting the coupling between radial and angular momenta. We analyze the total kinetic energy (TKE) distribution of binary reaction products in the 136 Xe + 208 Pb reaction at E c.m. =526 MeV and compare with experimental data. From time evolution of single-particle orbitals in TDHF, the radial diffusion coefficient is computed on a microscopic basis, while a phenomenological treatment is introduced for the radial friction coefficient. By solving the quantal diffusion equation for the radial linear momentum, the dispersion of the radial linear momentum is obtained, from which one can construct the TKE distribution. We find that the calculations provide a good description of the TKE distribution for strongly damped events with large energy losses, TKEL ≳ 150 MeV. However, the calculations underestimate the TKE distribution for smaller energy losses. Further studies are needed to improve the technical details of calculations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

Development of Bio-Oil Commodity Fuel as a Refinery Feedstock from High Impact Algae Biomass

A two-stage hydrothermal liquefaction (HTL) process was developed to 1) reduce nitrogen levels in algal oil, 2) generate a nitrogen rich stream with limited inhibitors for recycle and algae cultivation, and 3) improve downstream catalytic hydrodenitrogenation and hydrodeoxygenation of the algal oil to refinery intermediates. In the first stage, low temperature HTL was conducted at 125, 175, and 225°C at holding times ranging from 1 to 30 min (time at reaction temperature). A consortium of three algal strains, namely Chlorella sorokiniana, Chlorella minutissima, and Scenedesmus bijuga were used to grow and harvest biomass in a raceway system – this consortium is called the UGA Raceway strain throughout the report. Subsequent analysis of the final harvested product indicated that only two strains predominated in the final harvest - Chlorella sorokiniana and Scenedesmus bijuga. Two additional strains representing a high protein (Spirulina platensis) and high lipid algae (Nannochloropsis) strains were also used in this study. These strains were purchased from suppliers. S. platensis biomass was provided by Earthrise Nutritionals LLC (Calipatria, CA) in dry powder form with defined properties, and was stored in airtight packages at 4°C prior to use. A Nannochloropsis paste from Reed Mariculture was purchased and used in the two-stage HTL/HDO experiments. The solids and liquids from this low temperature HTL pretreatment step were separated and analyzed, leading to the following conclusions. Overall, these results indicate that low temperature HTL (200-250°C) at short residence times (5-15 min) can be used to lyse algae cells and remove/separate protein and nitrogen before subsequent higher temperature HTL (for lipid and other polymer hydrolysis) and HDO. The significant reduction in nitrogen when coupled with low protein/high lipid algae cultivation methods at scale could significantly improve downstream catalytic HDO results. However, significant barriers and knowledge gaps exist that must be overcome and understood. The ability of the separated protein/nitrogen rich aqueous stream to support algae cultivation needs to be verified (and the kinetics of growth measured). The kinetics of algae hydrothermal liquefaction on a mechanistic basis needs to be measured and understood. A better understanding of Maillard reactions during algae HTL is needed. And the impact of Maillard reaction products and incompletely hydrolyzed cell wall components on catalyst deactivation during HDO needs to be understood. Finally, an inexpensive HDO process and associated catalyst capable of converting the algal oil to hydrocarbons needs to be developed.

09 BIOMASS FUELS↗
NASA NTRS2013

A One-year, Short-Stay Crewed Mars Mission Using Bimodal Nuclear Thermal Electric Propulsion (BNTEP) - A Preliminary Assessment

A crewed mission to Mars poses a significant challenge in dealing with the physiological issues that arise with the crew being exposed to a near zero-gravity environment as well as significant solar and galactic radiation for such a long duration. While long surface stay missions exceeding 500 days are the ultimate goal for human Mars exploration, short round trip, short surface stay missions could be an important intermediate step that would allow NASA to demonstrate technology as well as study the physiological effects on the crew. However, for a 1-year round trip mission, the outbound and inbound hyperbolic velocity at Earth and Mars can be very large resulting in a significant propellant requirement for a high thrust system like Nuclear Thermal Propulsion (NTP). Similarly, a low thrust Nuclear Electric Propulsion (NEP) system requires high electrical power levels (10 megawatts electric (MWe) or more), plus advanced power conversion technology to achieve the lower specific mass values needed for such a mission. A Bimodal Nuclear Thermal Electric Propulsion (BNTEP) system is examined here that uses three high thrust Bimodal Nuclear Thermal Rocket (BNTR) engines allowing short departure and capture maneuvers. The engines also generate electrical power that drives a low thrust Electric Propulsion (EP) system used for efficient interplanetary transit. This combined system can help reduce the total launch mass, system and operational requirements that would otherwise be required for equivalent NEP or Solar Electric Propulsion (SEP) mission. The BNTEP system is a hybrid propulsion concept where the BNTR reactors operate in two separate modes. During high-thrust mode operation, each BNTR provides 10's of kilo-Newtons of thrust at reasonably high specific impulse (Isp) of 900 seconds for impulsive transplanetary injection and orbital insertion maneuvers. When in power generation/EP mode, the BNTR reactors are coupled to a Brayton power conversion system allowing each reactor to generate 100's of kWe of electrical power to a very high Isp (3000 s) EP thruster system for sustained vehicle acceleration and deceleration in heliocentric space.

Burke, Laura M.↗
DOE OSTI2015

Spectral energy distributions and masses of 304 M31 old star clusters

This paper presents CCD multicolor photometry for 304 old star clusters in the nearby spiral galaxy M31, from which the photometry of 55 star clusters is first obtained. The observations were carried out as a part of the Beijing–Arizona–Taiwan–Connecticut Multicolor Sky Survey from 1995 February to 2008 March, using 15 intermediate-band filters covering 3000–10000 Å. Detailed comparisons show that our photometry is in agreement with previous measurements. Based on the ages and metallicities from Caldwell et al. and the photometric measurements here, we estimated the clusters’ masses by comparing their multicolor photometry with stellar population synthesis models. The results show that the sample clusters have masses between ∼3×10{sup 4}M{sub ⊙} and ∼10{sup 7}M{sub ⊙} with a peak of ∼4×10{sup 5}M{sub ⊙}. The masses here are in good agreement with those in previous studies. Combined with the masses of young star clusters of M31 from Wang et al., we find that the peak mass of the old clusters is 10 times that of young clusters.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

RX GEMINORUM: PHOTOMETRIC SOLUTIONS, (NEARLY UNIFORM) GAINER ROTATION, DONOR RADIAL VELOCITY SOLUTION, NON-LTE ACCRETION DISK MODELS OF Hα EMISSION PROFILES, AND SECULAR LIGHT CURVE CHANGES IN THE 20TH CENTURY

We obtained full-orbit Iybvu intermediate-band photometry and CCD spectroscopy of the long-period Algol eclipsing binary RX Geminorum. Photometric solutions using the Wilson–Devinney code give a gainer rotation (hotter, mass-accreting component) about 15 times the synchronous rate. We describe a simple technique to detect departures from uniform rotation of the hotter component. These binaries radiate double-peaked Hα emission from a low-mass accretion disk around the gainer. We used an approximate non-LTE disk code to predict models in fair agreement with observations, except in the far wings of the emission profile, where the star–inner disk boundary layer emits extra radiation. Variations in Hα emission derive from modulations in the transfer rate. A study of times of minima during the 20th century suggests that a perturbing third body is present near RX Gem.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

Key Roles of Lewis Acid-base Pairs on ZnxZryOz in Direct Ethanol/Acetone to Isobutene Conversion

The effects of surface acidity on the cascade ethanol-to-isobutene conversion were studied using ZnxZryOz catalysts. The ethanol-to-isobutene reaction was found to be limited by the secondary reaction of the key intermediate, acetone, namely the acetone-to-isobutene reaction. Although the catalysts with coexisting Brønsted acidity could catalyze the rate-limiting acetone-to-isobutene reaction, the presence of Brønsted acidity is also detrimental. First, secondary isobutene isomerization is favored, producing a mixture of butene isomers. Second, undesired polymerization and coke formation prevail, leading to rapid catalyst deactivation. Most importantly, both steady-state and kinetic reaction studies as well as FTIR analysis of adsorbed acetone-d6 and D2O unambiguously showed that a highly active and selective nature of balanced Lewis acid-base pairs was masked by the coexisting Brønsted acidity in the aldolization and self-deoxygenation of acetone to isobutene. As a result, ZnxZryOz catalysts with only Lewis acid-base pairs were discovered, on which nearly a theoretical selectivity to isobutene (~88.9%) was successfully achieved, which has never been reported before. Moreover, the absence of Brønsted acidity in such ZnxZryOz catalysts also eliminates the side isobutene isomerization and undesired polymerization/coke reactions, resulting in the production of high purity isobutene with significantly improved catalyst stability (< 2% activity loss after 200 h time-on-stream). This work not only demonstrates a balanced Lewis acid-base pair for the highly active and selective cascade ethanol-to-isobutene reaction, but also sheds light on the rational design of selective and robust acid-base catalyst for C-C coupling via aldolization reaction.

acetone↗
DOE OSTI2016

ON THE RR LYRAE STARS IN GLOBULARS. IV. ω CENTAURI OPTICAL UBVRI PHOTOMETRY

New accurate and homogeneous optical UBVRI photometry has been obtained for variable stars in the Galactic globular cluster ω Cen (NGC 5139). We secured 8202 CCD images covering a time interval of 24 years and a sky area of 84 × 48 arcmin. The current data were complemented with data available in the literature and provided new, homogeneous pulsation parameters (mean magnitudes, luminosity amplitudes, periods) for 187 candidate ω Cen RR Lyrae (RRLs). Among them we have 101 RRc (first overtone) and 85 RRab (fundamental) variables, and a single candidate RRd (double-mode) variable. Candidate Blazhko RRLs show periods and colors that are intermediate between the RRc and RRab variables, suggesting that they are transitional objects. A comparison of the period distribution and the Bailey diagram indicates that RRLs in ω Cen show a long-period tail not present in typical Oosterhoff II (OoII) globulars. The RRLs in dwarf spheroidals and in ultra-faint dwarfs have properties between Oosterhoff intermediate and OoII clusters. Metallicity plays a key role in shaping the above evidence. These findings do not support the hypothesis that ω Cen is the core remnant of a spoiled dwarf galaxy. Using optical period–Wesenheit relations that are reddening-free and minimally dependent on metallicity we find a mean distance to ω Cen of 13.71 ± 0.08 ± 0.01 mag (semi-empirical and theoretical calibrations). Finally, we invert the I -band period–luminosity–metallicity relation to estimate individual RRLs’ metal abundances. The metallicity distribution agrees quite well with spectroscopic and photometric metallicity estimates available in the literature.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Structural and Kinetic Studies of Novel Cytochrome P450 Small-Alkane Hydroxylases

The goals of this project are to investigate (1) the kinetics and stabilities of engineered cytochrome P450 (P450) small alkane hydroxylases and their evolutionary intermediates, (2) the structural basis for catalytic proficiency on small alkanes of these engineered P450s, and (3) the changes in redox control resulting from protein engineering. To reach these goals, we have established new methods for determining the kinetics and stabilities of multicomponent P450s such as CYP153A6. Using these, we were able to determine that CYP153A6 is proficient for hydroxylation of alkanes as small as ethane, an activity that has never been observed previously in any natural P450. To elucidate the structures of the engineered P450s, we obtained x-ray diffraction data for two variants in the P450 PMO (propane monooxygenase) lineage and a preliminary structure for the most evolved variant. This structure shows changes in the substrate binding regions of the enzyme and a reduction in active site volume that are consistent with the observed changes in substrate specificity from fatty acids in the native enzyme to small alkanes in P450 PMO . We also constructed semi-rational designed libraries mutating only residues in the enzyme active site that in one round of mutagenesis and screening produced variants that achieved nearly half of the activity of the most evolved enzymes of the P450 PMO lineage. Finally, we found that changes in redox properties of the laboratory-evolved P450 alkane hydroxylases did not reflect the improvement in their electron transfer efficiency. The heme redox potential remained constant throughout evolution, while activity increased and coupling efficiency improved from 10% to 90%. The lack of correlation between heme redox potential and enzyme activity and coupling efficiency led us to search for other enzyme properties that could be better predictors for activity towards small alkanes, specifically methane. We investigated the oxidation potential of the radical oxidants of various P450s directly using a chemical approach to generate the radical in situ . This resulted in the first report of direct methane to methanol conversion by a heme porphyrin catalyst using the soluble P450 from Mycobacterium sp , CYP153A6.

03 NATURAL GAS↗
DOE OSTI2022

Thioester synthesis by a designed nickel enzyme models prebiotic energy conversion

The formation of carbon–carbon bonds from prebiotic precursors such as carbon dioxide represents the foundation of all primordial life processes. In extant organisms, this reaction is carried out by the carbon monoxide dehydrogenase (CODH)/acetyl coenzyme A synthase (ACS) enzyme, which performs the cornerstone reaction in the ancient Wood–Ljungdahl metabolic pathway to synthesize the key biological metabolite, acetyl-CoA. Despite its significance, a fundamental understanding of this transformation is lacking, hampering efforts to harness analogous chemistry. To address these knowledge gaps, we have designed an artificial metalloenzyme within the azurin protein scaffold as a structural, functional, and mechanistic model of ACS. We demonstrate the intermediacy of the Ni I species and requirement for ordered substrate binding in the bioorganometallic carbon–carbon bond-forming reaction from the one-carbon ACS substrates. The electronic and geometric structures of the nickel-acetyl intermediate have been characterized using time-resolved optical, electron paramagnetic resonance, and X-ray absorption spectroscopy in conjunction with quantum chemical calculations. Moreover, we demonstrate that the nickel-acetyl species is chemically competent for selective acyl transfer upon thiol addition to biosynthesize an activated thioester. Drawing an analogy to the native enzyme, a mechanism for thioester generation by this ACS model has been proposed. The fundamental insight into the enzymatic process provided by this rudimentary ACS model has implications for the evolution of primitive ACS-like proteins. Ultimately, these findings offer strategies for development of highly active catalysts for sustainable generation of liquid fuels from one-carbon substrates, with potential for broad applications across diverse fields ranging from energy storage to environmental remediation.

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

Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases

Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals and radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign rules. Thus, LCs/LACs provide a consistent description of CIDNP in both liquids and solids with the prospect of exploiting it for the analysis of short-lived radicals and for optimizing the polarization level.

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

REVERBERATION AND PHOTOIONIZATION ESTIMATES OF THE BROAD-LINE REGION RADIUS IN LOW-z QUASARS

Black hole mass estimation in quasars, especially at high redshift, involves the use of single-epoch spectra with signal-to-noise ratio and resolution that permit accurate measurement of the width of a broad line assumed to be a reliable virial estimator. Coupled with an estimate of the radius of the broad-line region (BLR) this yields the black hole mass M{sub BH}. The radius of the BLR may be inferred from an extrapolation of the correlation between source luminosity and reverberation-derived r{sub BLR} measures (the so-called Kaspi relation involving about 60 low-z sources). We are exploring a different method for estimating r{sub BLR} directly from inferred physical conditions in the BLR of each source. We report here on a comparison of r{sub BLR} estimates that come from our method and from reverberation mapping. Our ''photoionization'' method employs diagnostic line intensity ratios in the rest-frame range 1400-2000 A (Al III {lambda}1860/Si III] {lambda}1892, C IV {lambda}1549/Al III {lambda}1860) that enable derivation of the product of density and ionization parameter with the BLR distance derived from the definition of the ionization parameter. We find good agreement between our estimates of the density, ionization parameter, and r{sub BLR} and those from reverberation mapping. We suggest empirical corrections to improve the agreement between individual photoionization-derived r{sub BLR} values and those obtained from reverberation mapping. The results in this paper can be exploited to estimate M{sub BH} for large samples of high-z quasars using an appropriate virial broadening estimator. We show that the width of the UV intermediate emission lines are consistent with the width of H{beta}, thereby providing a reliable virial broadening estimator that can be measured in large samples of high-z quasars.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2013

A One-year, Short-Stay Crewed Mars Mission Using Bimodal Nuclear Thermal Electric Propulsion (BNTEP) - A Preliminary Assessment

A crewed mission to Mars poses a signi cant challenge in dealing with the physiolog- ical issues that arise with the crew being exposed to a near zero-gravity environment as well as signi cant solar and galactic radiation for such a long duration. While long sur- face stay missions exceeding 500 days are the ultimate goal for human Mars exploration, short round trip, short surface stay missions could be an important intermediate step that would allow NASA to demonstrate technology as well as study the physiological e ects on the crew. However, for a 1-year round trip mission, the outbound and inbound hy- perbolic velocity at Earth and Mars can be very large resulting in a signi cant propellant requirement for a high thrust system like Nuclear Thermal Propulsion (NTP). Similarly, a low thrust Nuclear Electric Propulsion (NEP) system requires high electrical power lev- els (10 megawatts electric (MWe) or more), plus advanced power conversion technology to achieve the lower speci c mass values needed for such a mission. A Bimodal Nuclear Thermal Electric Propulsion (BNTEP) system is examined here that uses three high thrust Bimodal Nuclear Thermal Rocket (BNTR) engines allowing short departure and capture maneuvers. The engines also generate electrical power that drives a low thrust Electric Propulsion (EP) system used for ecient interplanetary transit. This combined system can help reduce the total launch mass, system and operational requirements that would otherwise be required for equivalent NEP or Solar Electric Propulsion (SEP) mission. The BNTEP system is a hybrid propulsion concept where the BNTR reactors operate in two separate modes. During high-thrust mode operation, each BNTR provides 10's of kilo- Newtons of thrust at reasonably high speci c impulse (Isp) of 900 seconds for impulsive trans-planetary injection and orbital insertion maneuvers. When in power generation / EP mode, the BNTR reactors are coupled to a Brayton power conversion system allowing each reactor to generate 100's of kWe of electrical power to a very high Isp (3000 s) EP thruster system for sustained vehicle acceleration and deceleration in heliocentric space.

Burke, Laura A.↗
DOE OSTI2012

Bis-pi-allylpalladium Complexes in Catalysis of Multicomponent Reactions (Final Report)

The research project involved the development of new and functionally improved Pd(II) catalyst for a three-component reaction of boronic acids, allenes and imines to afford homoallylic amines that are useful in synthesis of biologically active heterocycles. Furthermore, insights into the reaction mechanism and the structure and reactivity of the catalytically active intermediates involved in this process were sought. As a result of this work, a new type of Pd-catalysts possessing an auxiliary ligand attached to the Pd center via a C-Pd and N-Pd bonds were identified, and found to be more active than the traditional catalysts derived from Pd(OAc) 2 . The new catalysts provided an access to a broader range of homoallylic amine products. Although the final unequivocal evidence regarding the structure of the Pd(II) complex involved in the nucleophilic transfer of the allyl fragment from the palladium center to the imine could not be obtained, mechanistic insights into the events that are detrimental to the activity of the originally reported Pd(OAc) 2 -based catalytic systems were uncovered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory-based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH 2 OO, CH 3 CHOO, (CH 3 ) 2 COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene-derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH 2 OO and (CH 3 ) 2 COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever-growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing 1 ππ* state, and how this varies with CI, with conformer and with excitation wavelength. Furthermore, the later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo-induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non-adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation

Metallocenes, including their permethylated variants, are extremely important in organometallic chemistry. In particular, many are synthetically useful either as oxidants (e.g., Cp 2 Fe + ) or as reductants (e.g., Cp 2 Co, Cp* 2 Co, and Cp* 2 Cr). The latter have proven to be useful reagents in the reductive protonation of small-molecule substrates, including N 2 . As such, understanding the behavior of these metallocenes in the presence of acids is paramount. In the present study, we undertake the rigorous characterization of the protonation products of Cp* 2 Co using pulse electron paramagnetic resonance (EPR) techniques at low temperature. We provide unequivocal evidence for the formation of the ring-protonated isomers Cp*(exo/endo-η 4 -C 5 Me 5 H)Co + . Variable temperature Q-band (34 GHz) pulse EPR spectroscopy, in conjunction with density functional theory (DFT) predictions, are key to reliably assigning the Cp*(exo/endo-η 4 -C 5 Me 5 H)Co + species. We also demonstrate that exo-protonation selectivity can be favored by using a bulkier acid and suggest this species is thus likely a relevant intermediate during catalytic nitrogen fixation given the bulky anilinium acids employed. Of further interest, we provide physical data to experimentally assess the C–H bond dissociation free energy (BDFE C–H ) for Cp*(exo-η 4 -C 5 Me 5 H)Co + . These experimental data support our prior DFT predictions of an exceptionally weak C–H bond (<29 kcal mol –1 ), making this system among the most reactive (with respect to C–H bond strength) to be thoroughly characterized. Furthermore, these data also point to the propensity of Cp*(exo-η 4 -C 5 Me 5 H)Co to mediate hydride (H – ) transfer. Our findings are not limited to the present protonated metallocene system. Accordingly, we outline an approach to rationalizing the reactivity of arene-protonated metal species, using decamethylnickelocene as an additional example.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

X-ray diagnostic developments in the perspective of DEMO

Soft X-ray diagnostics at present are not adequate for a burning plasma experiment, neither in term of hardware nor as diagnostic conception. Detectors have to be radiation tolerant, easily shielded, with low sensitivity to neutrons and gammas and with energy discrimination. Layout and viewing capability should be more flexible, thanks to the use also of optical devices, going toward a configuration intermediate between discrete tomography and pure imaging. The general conception of these diagnostics should therefore evolve in the direction of pattern recognition for a real time feedback. This work is focused on the diagnostic developments undertaken at the ENEA- Frascati X-ray Laboratory, following in particular three directions: gas detector for fast and advanced high density tomography, C-MOS solid state imaging detectors for slow control and X-ray polycapillary optics. GEM gas detectors in photon counting mode (noise free) were developed in the range 1-30 keV having high efficiency, high time resolution (up to microseconds), energy discrimination in bands and optical flexibility. Discrimination of X-rays, neutrons and gammas has been demonstrated, thanks to the combination of intrinsic gain and discrimination thresholds, at neutron fluxes (10{sup 7} n/s*cm{sup 2}) comparable with the expected ones at the ports of ITER. GEM detectors are also extremely flexible in the design, allowing optimization of the measurements and solutions for shielding or minimization of the effect of background radiation. Two solid state C-MOS imagers working in photon counting mode, one based on Si semiconductor (Medipix-2, range 5-30 keV) and the other one having a CdTe sensor (Pixirad, range 2-100 keV) have been characterized in laboratory. C-MOS imagers have features and performances thoroughly complementary to the GEM detector and, thanks to their higher pixel density, could be used as remote imaging detectors coupled to optics. X-ray polycapillary lenses have been therefore studied in the laboratory both as imaging optical device (full lens) or to define a line of sight (cylinder lens); the preliminary results are encouraging toward the goal of using these lenses to transport X-ray radiation far from the reactor. Reflective or diffractive X-ray optics can be also an option for tomography. A GEM detector has been installed at KSTAR and in the next future hopefully the other approaches will be tested there: once their feasibility will be demonstrated, the issue of the improvement of the radiation tolerance will be faced and the development of algorithms for data analysis as well.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗