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At least 271 records · Page 15

Alignment Thresholds of Molecules

Molecules have long been known to align in moderately intense, far off-resonance laser fields with a large variety of applications in physics and optics. Here, we illustrate and describe the physical origin of a previously unexplored phenomenon in the adiabatic alignment dynamics of molecules, which is fundamentally interesting and also has an important practical implication. Specifically, the intensity dependence of the degree of adiabatic alignment exhibits a threshold behavior, below which molecules are isotropically distributed rotationally and above which the alignment rapidly reaches a plateau. Furthermore, we show that both the intensity and the temperature dependencies of the alignment of all linear molecules exhibit universal curves and derive analytical forms to describe these dependencies. Finally, we illustrate that the alignment threshold occurs very generally at a lower intensity than the off-resonance ionization threshold, a numerical observation that is readily illustrated analytically. The threshold behavior is attributed to a tunneling mechanism that rapidly switches off at the threshold intensity, where tunneling between the potential wells corresponding to the two orientations of the aligned molecules becomes impossible. The universal threshold behavior of molecular alignment is a simple phenomenon, but one that was not realized before and can be readily tested experimentally.

74 ATOMIC AND MOLECULAR PHYSICS↗

Aggressive Mammary Cancers Lacking Lymphocytic Infiltration Arise in Irradiated Mice and Can Be Prevented by Dietary Intervention

Because the incidence of breast cancer increases decades after ionizing radiation exposure, aging has been implicated in the evolution of the tumor microenvironment and tumor progression. In this paper, we investigated radiation-induced carcinogenesis using a model in which the mammary glands of 10-month-old BALB/c mice were transplanted with Trp53-null mammary tissue 3 days after exposure to low doses of sparsely ionizing γ-radiation or densely ionizing particle radiation. Mammary transplants in aged, irradiated hosts gave rise to significantly more tumors that grew more rapidly than those in sham-irradiated mice, with the most pronounced effects seen in mice irradiated with densely ionizing particle radiation. Tumor transcriptomes identified a characteristic immune signature of these aggressive cancers. Consistent with this, fast-growing tumors exhibited an immunosuppressive tumor microenvironment with few infiltrating lymphocytes, abundant immunosuppressive myeloid cells, and high COX-2 and TGFβ. Only irradiated hosts gave rise to tumors lacking cytotoxic CD8 + lymphocytes (defined here as immune desert), which also occurred in younger irradiated hosts. These data suggest that host irradiation may promote immunosuppression. To test this, young chimera mice were fed chow containing a honeybee-derived compound with anti-inflammatory and immunomodulatory properties, caffeic acid phenethyl ester (CAPE). CAPE prevented the detrimental effects of host irradiation on tumor growth rate, immune signature, and immunosuppression. These data indicated that low-dose radiation, particularly densely ionizing exposure of aged mice, promoted more aggressive cancers by suppressing antitumor immunity. Dietary intervention with a nontoxic immunomodulatory agent could prevent systemic effects of radiation that fuel carcinogenesis, supporting the potential of this strategy for cancer prevention.

60 APPLIED LIFE SCIENCES↗

Quantitative Determination of Total Cesium in Savannah River Site (SRS) Tank Waste by Inductively Coupled Plasma Emission Spectroscropy

Utilization of the significant and unique wavelength dynamic range (165 to 1100 nm) available on the Leeman Prodigy Inductively Coupled Plasma Emission Spectroscopy (ICP-ES) allows for quantification of cesium using the emission line 894.347 nm without the potential of Barium interference in nuclear waste samples. Samples are added to a Sodium Peroxide Fusion and Lithium Carbonate buffer in 2% nitric acid solution to increase sensitivity of the easily ionizable (<6 eV) cesium for quantitation to 5 pbb. Through direct comparison of analytical data results, the method is proven to be complementary to the Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis (LOQ 100 ppt) in support of the Department of Energy’s (DOE) Nuclear Waste Mission.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electronic states and transitions of PrO and PrO + probed by threshold ionization spectroscopy and spin–orbit multiconfiguration perturbation theory

The precise ionization energy of praseodymium oxide (PrO) seeded in supersonic molecular beams is measured with mass-analyzed threshold ionization (MATI) spectroscopy. Here, a total of 33 spin–orbit (SO) states of PrO and 23 SO states of PrO + are predicted by second-order multiconfigurational quasi-degenerate perturbation (MCQDPT2) theory. Electronic transitions from four low-energy SO levels of the neutral molecule to the ground state of the singly charged cation are identified by combining the MATI spectroscopic measurements with the MCQDPT2 calculations. The precise ionization energy is used to reassess the ionization energies and the reaction enthalpies of the Pr + O → PrO + + e – chemi-ionization reaction reported in the literature. An empirical formula that uses atomic electronic parameters is proposed to predict the ionization energies of lanthanide monoxides, and the empirical calculations match well with available precise experimental measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of delta ray electrons on measurement uncertainties of harp system

A harp system, which is a multi-wire beam profile monitoring (MWPM) system, is planned upstream of the spallation target to make in situ calibration of beam current density configuration on the target along with beam imaging from luminescent coating on the beam entrance window at the Second Target Station (STS) of the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL). This beam interception-based beam diagnostics system on the target will be used to ensure that the maximum beam loads on the target are within the design range during neutron production. Current design of the harp consists of three layers of measurement wires each of which is sandwiched between voltage biasing wire planes. The signal obtained from each measurement wire layer is disturbed by secondary electrons (SE) and delta rays produced by beam-matter interactions in neighboring wires and ionization of residual gases in accelerator vacuum. While the backgrounds from SE can be suppressed by voltage biasing, the delta-ray electrons with kinetic energies above keV ranges overcome the electric potential bias. In this paper, we study the effects of delta-rays on the measurement uncertainties of MWPM using the particle transport simulation code FLUKA. Furthermore, the cases where the harp system is installed in the proximity of a large delta ray sources such as proton beam window or in the core vessel filled with sub-atmospheric gas have been studied.

Lee, Yong Joong↗

A Critical Review of Radiolysis Issues in Water-Cooled Fission and Fusion Reactors: Part I, Assessment of Radiolysis Models

A critical review is presented on modeling of the radiolysis of the coolant water in nuclear power reactors with emphasis on ITER. The review is presented in two parts: In Part I, we assess previous work in terms of compliance with important chemical principles and conclude that no model proposed to date is completely satisfactory, in this regard. Thus, some reactions that have been proposed in various radiolysis models are not elementary in nature and can be decomposed into two or more elementary reactions, some of which are already included in the models. These reactions must be removed in formulating a viable model. Furthermore, elementary reactions between species of like charge are also commonly included, but they can be discounted upon the basis of Coulombic repulsion under the prevailing conditions (T < 350 °C) and must also be removed. Likewise, it is concluded that the current state of knowledge with respect to radiolytic yields (i.e., G-values) is also unsatisfactory. More work is required to ensure that the yields used in radiolysis models are truly “primary” yields corresponding to a time scale of nanoseconds or less. This is necessary to ensure that the impact of the reactions that occur outside of the spurs (ionizing particle tracks in the medium) are not counted twice. In Part II, the authors review the use of the radiolysis models coupled with electrochemical models to predict the water chemistry, corrosion potential, crack growth rate in Type 304 SS, and accumulated damage in the coolant circuits of boiling water reactors, pressurized water reactors, and the test fusion reactor, ITER. Based on experience with fission reactors, the emphasis should be placed on the control of the electrochemical corrosion potential because it is the parameter that best describes the state of corrosion in coolant circuits.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Ambient Mass Spectrometry Rapid Analysis Methods for Trace Inorganics

The ability to rapidly detect and characterize the chemistry of trace quantities of inorganic species has multiple potential applications, including nuclear safeguards, nuclear forensics, and environmental monitoring. Some mass spectrometric methods currently exist, but they are costly and time-intensive, often destroying chemical information in the process of ionization. Ambient mass spectrometry is a relatively new analytical method in which samples are introduced to the mass spectrometer from atmospheric pressure, rather than from high vacuum. Ambient MS can operate with gentler ionization methods such as electrospray ionization (ESI) and paper-spray ionization (PSI), reducing fragmentation and preserving the chemical information of the analyte. This may be useful for determining the intended purpose of material in a sample. Strontium, part of nuclear fallout, is analyzed here to test these new analytical methods for viability. Electrospray ionization mass spectrometry functions by spraying the sample as a solution through a needle charged to a few kV. A nebulizing gas flows out along with the sample to create the spray before droplets enter a drying chamber with heated drying gas to remove the solvent molecules. From there bare analyte ions enter the mass spectrometer. This method has the advantage of relatively fast sample preparation and stable ionization. More stable ionization produces higher-quality data. Paper-spray ionization mass spectrometry operates by applying sample to a paper triangle. The paper triangle is then electrified in a metal clamp to a few kV before spray solvent is applied. The spray solvent transports analyte in the sample to the tip, where it is ionized and enters the mass spectrometer. One advantage of this method is reduced sample preparation - an analyst can even swipe a surface and cut a triangle directly from the swipe. The data analysis serves to rapidly process tens of samples all at once. The mass spectrometer outputs a file containing a few hundred spectra for each sample. The pipeline processes each one to identify peaks of interest. A full palette of data analysis metrics are generated, including plots of the raw data and plots of calculated values such as isotopic ratios. The pipeline filters the raw data to remove noise and background peaks, as well as peaks representing detector saturation. A heat map is generated to show the overall spectrum in mass-time- intensity space. Post-processing, we obtained the desired calibration curves, demonstrating that both ESI-MS and PSI-MS are viable methods for quantifying trace amounts of inorganics while retaining their chemical speciation information. ESI-MS demonstrated a linear response region of 100 ppb to 20 ppm, with a limit-of-detection of around 100 ppb. At top left is an example spectrum with the {sup 88}SrNO{sub 3} peak identified to show the retention of chemical speciation. PSI-MS showed a linear response region of around 1 ppb to 1 ppm, with a limit-of-detection of near 1 ppb. PSI-MS produced more erratic results than ESI-MS, likely due to the variability in ionization resulting from manual positioning of the paper triangle near the MS inlet. Future efforts will focus on improving the repeatability of PSI-MS as well as analyzing other species of interest such as cerium and uranium. Improvements will also be made to create more reliable data extraction and intelligent data filtering.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mode transitions and spoke structures in E × B Penning discharge

Two-dimensional particle-in-cell simulations in the (radial-azimuthal) plane perpendicular to the axial direction of a cylindrical $E$ x $B$ Penning discharge are presented. The low-pressure discharge is self-consistently supported by plasma ionization from the electron beam injected axially, along the direction of the external magnetic field. It is shown that with the increasing strength of the external magnetic field, the discharge undergoes a sequence of transitions between several azimuthal modes. Azimuthal m > 1 spiral arm structures are excited at low magnetic field values as plasma confinement improves and the radial density profile becomes peaked. With a larger field, spiral arms with m > 1 are replaced by the m = 1 spoke mode, most clearly seen in plasma density. A transition from spiral arms to the spoke regime occurs when the plasma potential in the center changes from weakly positive (or zero) to negative. Further increase in the magnetic field results in a well-developed m = 1 spoke mode with additional small-scale higher-frequency m > 1 structures inside and around the spoke. It is shown that while ionization and collisions affect some characteristics of the observed fluctuations, the basic features of the spoke and m > 1 spiral structure remained similar without ionization. The role of energy conservation in small-scale high-frequency modes and spoke dynamics is discussed. It is demonstrated that in regimes with the m = 1 spoke mode, additional m = 4 harmonics of the ion and electron fluxes to the wall appear due to the square boundary. The frequency of the m = 1 mode is weakly affected by the geometry of the boundary.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗

An Experimental and Theoretical Study of the Valence Shell Electronic Structure of Nitromethane

Vibrationally resolved CH 3 NO 2 and CD 3 NO 2 photoelectron spectra and angular distribution parameters, β, have been measured in the photon energy range 20–80 eV. This allows a comprehensive investigation of conflicting literature interpretations of the two outermost photoelectron bands, complemented by high-level calculations characterizing the three O lone-pair-based orbital ionizations expected in this region. Franck–Condon simulations allow the regular vibrational progressions observed at the beginning of the first and second bands to be assigned as predominantly modes v 5 and v 6 of the D 0 and D 2 cation states, respectively. Irregular structuring observed midband in both bands is attributed to avoided crossings between the adiabatic D 0 /D 1 and D 1 /D 2 states as identified in potential surface cuts taken along the v 5 and v 6 normal mode coordinates. The associated D 0 /D 1 and D 1 /D 2 conical intersections were located and characterized, allowing possible vibronic coupling and its impact on the photoelectron spectra of the D 0 , D 1 , and D 2 states to be discussed. This helps rationalize the apparently missing D 1 ionization in this region, although some contribution by this state may be identifiable in the β-parameter spectra. Theoretical analysis of the complete valence region spectrum identifies the early breakdown of the independent electron model beyond these first two bands.

Powis, Ivan [University of Nottingham (United King↗

The effects of neutron and ionizing irradiation on the aqueous corrosion of SiC

Chemical vapor deposited (CVD) SiC and nuclear-grade SiC/SiC composite materials were exposed to light water reactor (LWR) conditions at the MIT Nuclear Reactor (MITR) here. Three sets of samples were exposed within flowing PWR-chemistry-coolant under either 1) neutron and ionizing irradiation with resulting radiolysis products, 2) radiolysis products without neutron flux, 3) loop coolant. Post-irradiation examination (PIE) exhibited an increase in corrosion from radiolysis products (particularly H 2 O 2 ), and potentially a further increase from radiation damage. For CVD SiC, regardless of exposure location, the in-situ observed corrosion rate was less than 1 µm per year, potentially within acceptable limits for LWR application.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hydrolysis of Acetamide on Low-Index CeO 2 Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Using DFT calculations and acetamide as the main example, we show that ceria is a potential catalyst for the hydrolysis of amide and similar bonds. The overall reaction is endergonic in the gas phase, yielding acetic acid and ammonia, but is slightly exergonic in the aqueous phase, which facilitates ionization of the products (CH 3 COO – and NH 4 + ). Neighboring Ce and O sites on the CeO 2 (111), (110), and (100) facets are conducive to the formation of an activated metastable tetrahedral intermediate (TI) complex, followed by C–N bond scission. With van der Waals and solvation effects taken into account, the overall reaction energetics is found to be most favorable on the (111) facet as desorption of acetic acid is much more uphill energetically on (110) and (100). We further suggest that the Ce–O–Ce sites on ceria surfaces can activate X(=Y)–Z type bonds in amides, amidines, and carboxylate and phosphate esters, among many others that we term “generalized esters”. A Brønsted-Evans–Polanyi relationship is identified correlating the stability of the transition and final states of the X–Z generalized ester bond scission. A simple descriptor (ΣΔχ) based on the electronegativity of the atoms that constitute the bond (X, Y, Z) versus those of the catalytic site (O, Ce, Ce) captures the trend in the stability of the transition state of generalized ester bond scission and suggests a direction for modifying ceria for targeting specific organic substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Search by the SENSEI Experiment for Millicharged Particles Produced in the NuMI Beam

Millicharged particles appear in several extensions of the standard model, but have not yet been detected. These hypothetical particles could be produced by an intense proton beam striking a fixed target. We use data collected in 2020 by the SENSEI experiment in the MINOS cavern at the Fermi National Accelerator Laboratory to search for ultrarelativistic millicharged particles produced in collisions of protons in the NuMI beam with a fixed graphite target. The absence of any ionization events with 3 to 6 electrons in the SENSEI data allow us to place world-leading constraints on millicharged particles for masses between 30 to 380 MeV. This work also demonstrates the potential of utilizing low-threshold detectors to investigate new particles in beam-dump experiments, and motivates a future experiment designed specifically for this purpose. Published by the American Physical Society 2024

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Noninvasive Detection, Tracking, and Characterization of Aerogel Implants Using Diagnostic Ultrasound

Medical implants are routinely tracked and monitored using different techniques, such as MRI, X-ray, and ultrasound. Due to the need for ionizing radiation, the two former methods pose a significant risk to tissue. Ultrasound imaging, however, is non-invasive and presents no known risk to human tissue. Aerogels are an emerging material with great potential in biomedical implants. While qualitative observation of ultrasound images by experts can already provide a lot of information about the implants and the surrounding structures, this paper describes the development and study of two simple B-Mode image analysis techniques based on attenuation measurements and echogenicity comparisons, which can further enhance the study of the biological tissues and implants, especially of different types of biocompatible aerogels.

36 MATERIALS SCIENCE↗

CO 2 –Based Dual–Tone Resists for Electron Beam Lithography

The increasing global environmental and energy crisis has urgently motivated the advancement of sustainable materials. Significant effort has been focused on developing new materials to replace the fossil-based resists in the semiconductor industry based on greener sources such as ice, dry ice, small organic molecules, and proteins. Such resist materials, however, have yet to meet the stringent requirements of high sensitivity, high resolution, reliable repeatability, and good compatibility with the current protocols. To this end, CO 2 -based polycarbonates (CO 2 -PCs) obtained from the copolymerization of CO 2 and epoxides are demonstrated as sustainable dual-tone (positive & negative tone) resists for electron beam lithography. By adjusting the chemical structure, developing agent, and molecular weight, the CO 2 -PCs present high sensitivities to electron beam (1.3/120 μC cm -2 ), narrow critical dimensions (29/58 nm), and moderate line edge roughness (4.6/26.7 nm) for negative and positive resists, respectively. Here, a deep understanding of the exposure mechanism of CO 2 -PC resists is provided on the basis of the Fourier transform infrared, Raman, and electron ionization mass spectroscopy. 2D photonic crystal devices are fabricated using the negative and positive CO 2 -PC resists, respectively, and both devices show distinct colors derived from their well-defined nanostructures, indicating the great practical potential of CO 2 -derived electron beam resists.

nanofabrication↗

Modifications produced on a large magnetized plasma column by a floating end-plate that is partially emissive: Experiment and theory

An experiment is performed on a large plasma device operated by the Basic Plasma Science Facility at the University of California, Los Angeles, in which an electrically floating structure is placed near the end of the 18-m magnetized plasma column. The structure consists of a flat carbon plate that acts as a mask for a smaller, ring-shaped LaB6 emissive surface whose temperature can be externally controlled. This configuration has been previously used to study electron heat transport and pressure-driven avalanches [B. Van Compernolle and G. J. Morales, Phys. Plasmas 24, 112302 (2017)] by biasing the LaB6 ring-cathode with respect to a distant anode in a cold afterglow plasma. In contrast, the present study is performed during the active portion of the steady-state discharge in which the nominal plasma parameters are determined by the injection of an electron beam from a BaO cathode at the opposite end. It is found that, even without an applied bias on the LaB6 cathode, the self-consistent potential and current profiles are modified near the end plate as the LaB6 temperature is increased, resulting in density increases on the field lines in contact with the ring-cathode. In the absence of enhanced ionization, at the largest cathode temperatures, the ambient density can be doubled. A theoretical model is presented that provides a quantitative explanation for the experimental observations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Toward sustainable production of N-containing products via nonthermal plasma-enhanced conversion of natural gas resources

Nonthermal plasmas can directly activate and cleave the strong chemical bonds in molecular nitrogen and methane to facilitate the transformation of these inherently stable molecules through the application of electrical energy. Here, we report a low temperature, atmospheric pressure, nonthermal plasma for the “one-pot” synthesis of olefins, alkynes, higher molecular weight hydrocarbons, ammonia, and nitrogen-containing liquids from a representative shale gas feed enriched with nitrogen. Furthermore, we reproducibly observe a wide range of valuable and synthetically challenging gas-phase and liquid-phase products containing C-N, C-C, and N-H bonding by controlling the N 2 concentration in the inlet feed stream. In nitrogen-lean regimes, hydrocarbon products dominate (e.g., ethylene, acetylene, etc.), while nitrogen-rich regimes promote incorporation of nitrogen into the products, leading to the formation of ammonia and liquid products containing a variety of functionalities (e.g., nitriles, amines, heterocycles). High resolution electrospray ionization mass spectrometry was used to measure molecular weights and identify the chemical formulas of the liquid products. Van Krevelen diagrams were created and showed many products with compositions around H/C = 2 and N/C = 0.5, indicating the potential importance of intermediate species with these ratios for liquid formation (e.g., CH 3 CN + H).

03 NATURAL GAS↗

Lectures on statistical mechanics

Presented here is a transcription of the lecture notes from Professor Allan N. Kaufman’s graduate statistical mechanics course Physics 212A and 212B at the University of California Berkeley from the 1972–1973 academic year. 212A addressed equilibrium statistical mechanics with topics: fundamentals (micro-canonical and sub-canonical ensembles, adiabatic law and action conservation, fluctuations, pressure, and virial theorem), classical fluids and other systems (equation of state, deviations from ideality, virial coefficients and van der Waals potential, canonical ensemble and partition function, quasistatic evolution, grand-canonical ensemble and partition function, chemical potential, simple model of a phase transition, quantum virial expansion, numerical simulation of equations of state, and phase transition), chemical equilibrium (systems with multiple species and chemical reactions, law of mass action, Saha equation, chemical equilibrium including ionization and excited states), and long-range interactions (including Coulomb, dipole, and gravitational interactions, Debye–Hückel theory, and shielding). 212B addressed nonequilibrium statistical mechanics with topics: fundamentals (definitions: realizations, moments, characteristic function, and discrete variables), Brownian motion (Langevin equation, fluctuation–dissipation theorem, spatial diffusion, Boltzmann’s H-theorem), Liouville and Klimontovich equations, Landau equation (derivation, elaboration, and H-theorem, and irreversibility), Markov processes and Fokker–Planck equation (derivations of the Fokker–Planck equation and a master equation), linear response and transport theory (linear Boltzmann equation, linear response theory of Kubo and Mori, relation of entropy production to electrical conductivity, transport relations and coefficients, normal mode solutions of the transport equations, sketch of a generalized Langevin equation method for transport theory), and an introduction to nonequilibrium quantum statistical mechanics.

plasma dynamics↗