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Benchmark full configuration-interaction calculations on H2O, F- and F

Full configuration-interaction calculations are reported, and compared to other methods, for H2O at its equilibrium geometry and at two geometries with the H-O bonds stretched. Since the percentage of the self-consistent field (SCF) reference in the full configuration-interaction (FCI) wave function decreases greatly with the bond elongation, the accuracy of techniques based on a single reference do not compare well with the FCI results. However, the results from a complete active space SCF/multireference configuration-interaction (CASSCF/MRCI) treatment are in good agreement with the FCI. Correlation effects in F compared to Ne are far more similar than for F- compared to Ne, despite F- and Ne being isoelectronic. Since the importance of higher than double excitations is more important for F- than F, a very high percentage of the correlation must be obtained to accurately compute the electron affinity. In a CASSCF/MRCI treatment the higher than quadruple excitations contribute 0.02 eV to the electron affinity (EA), even for modest basis sets.

Bauschlicher, C. W., Jr.↗

High temperature conductivity of potassium-beta(double prime)-alumina

Potassium beta(double prime)-alumina (BDPA) single crystals have been reported by several groups to leave higher ionic conductivity than sodium BDPA crystals at room temperature, and similar conductivities are obtained at temperatures up to 600-700 K. Potassium BDPA ceramics have been reported to have significantly poorer conductivities than those of sodium BDPA ceramics, but conductivity measurements at temperatures above 625 K have not been reported. In this study, K(+)-BDPA ceramics were prepared from Na(+)-BDPA ceramic using a modified version of the exchange reaction with KCl vapor reported by Crosbie and Tennenhouse (1982), and the conductivity has been measured in K vapor at temperatures up to 1223 K, using the method of Cole et al. (1979). The results indicate reasonable agreement with earlier data on K(+)-BDPA ceramic measured in a liquid K cell, but show that the K(+)-BDPA ceramic's conductivity approaches that of Na(+)-BDPA ceramic at higher temperatures, being within a factor of four at 700 K and 60 percent of the conductivity of Na(+)-BDPA at T over 1000 K. Both four-probe dc conductivity and four probe ac impedance measurements were used to characterize the conductivity. A rather abrupt change in the grain boundary resistance suggesting a possible phase change in the intergranular material, potassium aluminate, is seen in the ac impedance behavior.

Williams, R. M.↗

Large Aperture Scanning Lidar Based on Holographic Optical Elements

Lidar remote sensing instruments can make a significant contribution to satisfying many of the required measurements of atmospheric and surface parameters for future spaceborne platforms, including topographic altimeters, atmospheric profiles of, wind, humidity, temperature, trace molecules, aerosols, and clouds. It is highly desirable to have wide measurement swaths for rapid coverage rather than just the narrow ribbon of data that is obtained with a nadir only observation. For most applications global coverage is required, and for wind measurements scanning or pointing is required in order to retrieve the full 3-D wind vector from multiple line-of-sight Doppler measurements. Conventional lidar receivers make up a substantial portion of the instrument's size and weight. Wide angle scanning typically requires a large scanning mirror in front of the receiver telescope, or pointing the entire telescope and aft optics assembly, Either of these methods entails the use of large bearings, motors, gearing and their associated electronics. Spaceborne instruments also need reaction wheels to counter the torque applied to the spacecraft by these motions. NASA has developed simplified conical scanning telescopes using Holographic Optical Elements (HOEs) to reduce the size, mass, angular momentum, and cost of scanning lidar systems. NASA has developed two operating lidar systems based on 40 cm diameter HOEs. The first such system, named Prototype Holographic Atmospheric Scanner for Environmental Remote Sensing (PHASERS) was a joint development between NASA Goddard Space Flight Center (GSFC) and the University of Maryland College Park. PHASERS is based on a reflection HOE for use at the doubled Nd:YAG laser wavelength of 532 nm and has recently undergone a number of design changes in a collaborative effort between GSFC and Saint Anselm College in New Hampshire. The next step was to develop IR transmission HOEs for use with the Nd:YAG fundamental in the Holographic Airborne Rotating Lidar Instrument Experiment (HARLIE). The HOE spins like a compact disk in a large ring ball bearing. In an aircraft the HOE faces down, looking out through a window at an angle of 45 degrees off-nadir. The HOE diffracts 85% of the incident 532 nm light into a 160 micron spot at a focal length of 1 meter. HARLIE is a field deployable lidar measuring aerosol, cloud, and boundary layer backscatter for atmospheric research. It has flown several times and is also used from a ground-based trailer in an upward-looking mode. The HOE generates a 45 degree conical scan pattern by rotating at speeds up to 30 rpm. Like PHASERS, the HOE in HARLIE serves both as the laser collimating lens as well as the receiver telescope primary optic. The telescope is coupled to the receiver package via fiber optic. The transmitter is a diode pumped Nd:YAG laser operating at 1064 nm, delivering 1 mJ pulses at a 5 KHz rep-rate. The receiver has a 200 microradian field-of-view and a 0.5 nm optical bandpass. The photon counting data system utilizes a single Geiger-mode silicon avalanche photodiode detector, This new technology has also presented us with new data visualization challenges as well as new measurement techniques. The backscatter data obtained from a stationary (i.e. ground-based) scanning HOE lidar is on the surface of a cone, which when viewed over many consecutive scans can reveal atmospheric motions on this surface over time as the atmosphere advects over the site. In a moving platform such as an airplane or satellite, the data from consecutive scans cover different areas under the flight path, revealing atmospheric structure in 3-dimensions. An example of a visualization of HARLIE ground-based data is presented, showing aerosol backscatter on a 90 degree conical surface generated from one 360 degree scan of the lidar during the HOLO-1 field campaign on the afternoon of 10 March 1999. Higher backscatter levels are rendered as lighter signal against a dark background. Breaking Kelvin-Helmholtz waves are evident on the north side of the scan at an altitude of 10-11 km. Time series of successive scans made at regular intervals render unique views of atmospheric motions, from which vertical profiles of atmospheric wind vectors can be obtained using a unique data analysis approach. Wind vectors obtained from the lidar were compared with co-located radiosonde wind profiles during an intensive operating period in September-October 2000 at the Atmospheric Radiation Measurement Program's Southern Great Plains Central Facility.

Schwemmer, Geary K.↗

Calculations of Solar Shortwave Heating Rates due to Black Carbon and Ozone Absorption Using in Situ Measurements

Results for the solar heating rates in ambient air due to absorption by black-carbon (BC) containing particles and ozone are presented as calculated from airborne observations made in the tropical tropopause layer (TTL) in January-February 2006. The method uses airborne in situ observations of BC particles, ozone and actinic flux. Total BC mass is obtained along the flight track by summing the masses of individually detected BC particles in the range 90 to 600-nm volume-equivalent diameter, which includes most of the BC mass. Ozone mixing ratios and upwelling and partial downwelling solar actinic fluxes were measured concurrently with BC mass. Two estimates used for the BC wavelength-dependent absorption cross section yielded similar heating rates. For mean altitudes of 16.5, 17.5, and 18.5 km (0.5 km) in the tropics, average BC heating rates were near 0.0002 K/d. Observed BC coatings on individual particles approximately double derived BC heating rates. Ozone heating rates exceeded BC heating rates by approximately a factor of 100 on average and at least a factor of 4, suggesting that BC heating rates in this region are negligible in comparison.

Gao, R. S.↗

Mosaic Cu I −Cu II −In III 2D Perovskites: Pressure‐Dependence of the Intervalence Charge Transfer and a Mechanochemical Alloying Method

Abstract The perovskite (BA) 4 [Cu II (Cu I In III ) 0.5 ]Cl 8 ( 1 BA ; BA + =butylammonium) allows us to study the high‐pressure structural, optical, and transport properties of a mixed‐valence 2D perovskite. Compressing 1 BA reduces the onset energy of Cu I/II intervalence charge transfer from 1.2 eV at ambient pressure to 0.2 eV at 21 GPa. The electronic conductivity of 1 BA increases by 4 orders of magnitude upon compression to 20 GPa, when the activation energy for conduction decreases to 0.16 eV. In contrast, Cu II perovskites achieve similar conductivity at ≈50 GPa. The solution‐state synthesis of these perovskites is complicated, with more undesirable side products likely from the precursor mixtures containing three different metal ions. To circumvent this problem, we demonstrate an efficient mechanochemical synthesis to expand this family of halide perovskites with complex composition by simply pulverizing together powders of 2D Cu II single perovskites and Cu I In III double perovskites.

Li, Jiayi↗

Characterize traction–separation relation and interfacial imperfections by data-driven machine learning models

Abstract Interfacial mechanical properties are important in composite materials and their applications, including vehicle structures, soft robotics, and aerospace. Determination of traction–separation (T–S) relations at interfaces in composites can lead to evaluations of structural reliability, mechanical robustness, and failures criteria. Accurate measurements on T–S relations remain challenging, since the interface interaction generally happens at microscale. With the emergence of machine learning (ML), data-driven model becomes an efficient method to predict the interfacial behaviors of composite materials and establish their mechanical models. Here, we combine ML, finite element analysis (FEA), and empirical experiments to develop data-driven models that characterize interfacial mechanical properties precisely. Specifically, eXtreme Gradient Boosting (XGBoost) multi-output regressions and classifier models are harnessed to investigate T–S relations and identify the imperfection locations at interface, respectively. The ML models are trained by macroscale force–displacement curves, which can be obtained from FEA and standard mechanical tests. The results show accurate predictions of T–S relations ( R 2 = 0.988) and identification of imperfection locations with 81% accuracy. Our models are experimentally validated by 3D printed double cantilever beam specimens from different materials. Furthermore, we provide a code package containing trained ML models, allowing other researchers to establish T–S relations for different material interfaces.

97 MATHEMATICS AND COMPUTING↗

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Online Optimization of NSLS-II Dynamic Aperture and Injection Transient (Facility Improvement Project)

The Facility Improvement Project (FIP) “Methods of online optimization of NSLS-II storage ring concurrent with user operations” proposed and approved in 2018 is now complete. The first goal is the online optimization of nonlinear beam dynamics to increase the beam lifetime and injection efficiency. We have developed a model-independent optimization technique using advanced algorithms. Using this technique, we increased the NSLS-II dynamic aperture by 20% and reduced the amplitude-dependent tune shift by a factor of two. We applied sextupole optimization to the new high-chromaticity lattice, which has been developed to improve the beam stability and to increase the single-bunch beam intensity. We were able to double the injection efficiency and exceed 90%. The second goal of this project is to provide the top-off injection with minimized perturbations of the beamline user operations. To achieve the transparent injection, we optimize the matching of four storage ring injection kickers reducing the perturbation of the stored beam orbit. The first application of the online optimization resulted in a reduction of the amplitude of residual beam oscillation by a factor of six, from 1300 μm down to 200 μm. Further improvement was limited by the timing jitter of the trigger boards. Then, we replaced all trigger boards with a new design and reduced the timing jitter by a factor of five, from 5 ns down to 1 ns. This upgrade resulted in the injection transient reduction from 200 μm to 120 μm. To optimize the full set of kicker parameters, including the trigger timing, amplitude, and pulse width, we upgraded all kicker power supplies with the capability of tunable waveform width. As a result, we have reduced the injection transient to the limit of 60 μm.

43 PARTICLE ACCELERATORS↗

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micrometers CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold ((is) approximately 4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3-m band are discussed.

Astrochemistry↗

Second-harmonic signature of chiral spin structures in W/Pt/Co heterostructures with tunable magnetic anisotropy

Abstract Second-harmonic Hall voltage (SHV) measurement method has been widely used to characterize the strengths of spin–orbit torques (SOTs) in heavy metal/ferromagnet thin films saturated in the single-domain regime. Here, we show that the magnetic anisotropy of a W/Pt/Co trilayer can be robustly tuned from in-plane to out-of-plane by varying W, Pt, or Co thicknesses. Moreover, in samples with easy-cone anisotropy, SHV measurements exhibit anomalous ‘humps’ in the multidomain regime accessed by applying a nearly out-of-plane external magnetic field. These hump features can only be explained as a result of the formation of Néel-type domain walls, efficiently driven by nevertheless small SOTs in this double heavy metal heterostructure with canceling spin Hall angles.

Physics↗

Search for Lepton Number Violation in 136 Xe and 134 Xe Decay

The EXO-200/nEXO group at Stony Brook University led by Krishna Kumar searched for neutrinoless double beta decay of 134 Xe and 136 Xe via participation in the final phase of the EXO-200 experiment and calibration pre-R&D for the next generation nEXO concept. On EXO-200, we carried out an improved analysis in the search for 134 Xe using data from Phase-II running. On nEXO, we completed a paper on our first phase of measurements demonstrating the feasibility of using photoelectricity from a gold photocathode to produce controlled amounts of charged clusters in liquid xenon. This has set the stage to develop a new test stand to evaluate the stability of a gold photocathode in order to explore the sensitivity of this method to monitor long electron lifetimes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

An Ensemble-Based Smoother with Retrospectively Updated Weights for Highly Nonlinear Systems

Monte Carlo computational methods have been introduced into data assimilation for nonlinear systems in order to alleviate the computational burden of updating and propagating the full probability distribution. By propagating an ensemble of representative states, algorithms like the ensemble Kalman filter (EnKF) and the resampled particle filter (RPF) rely on the existing modeling infrastructure to approximate the distribution based on the evolution of this ensemble. This work presents an ensemble-based smoother that is applicable to the Monte Carlo filtering schemes like EnKF and RPF. At the minor cost of retrospectively updating a set of weights for ensemble members, this smoother has demonstrated superior capabilities in state tracking for two highly nonlinear problems: the double-well potential and trivariate Lorenz systems. The algorithm does not require retrospective adaptation of the ensemble members themselves, and it is thus suited to a streaming operational mode. The accuracy of the proposed backward-update scheme in estimating non-Gaussian distributions is evaluated by comparison to the more accurate estimates provided by a Markov chain Monte Carlo algorithm.

Monte Carlo↗

Parallelized Convolutional Interleaver Implementation for Efficient DDR Memory Access

Convolutional interleavers are used in many different communications systems to correct for burst errors due to atmospheric fades and scintillation. The interleaver size is related to the channel coherence time and the data rate. Small convolutional interleavers can be implemented in a field programmable gate array (FPGA) block random access memory (BRAM). However, large interleavers exceeding the size of the BRAM on the FPGA are necessary for channels with longer fades and higher data rates. Therefore, an implementation utilizing double data rate (DDR) memory external to the FPGA is necessary. Wide DDR memory data buses can make the use of DDR memory for convolutional interleavers inefficient when individual symbols are written to and read from the memory. DDR memory operational speeds can also limit the data rate of the interleaver. The Consultative Committee for Space Data Systems (CCSDS) Optical Communications High Photon Efficiency (HPE) standard utilizes a convolutional channel symbol interleaver. A previous implementation of the HPE standard utilized BRAM for the convolutional interleaver, but mission requirements for the upcoming Optical Artemis-2 Orion (O2O) communications demonstration dictate the use of an interleaver exceeding the size of the BRAM. An algorithm and method for implementing the convolutional interleaver in the FPGA with DDR memory is described in this paper.

optical communications↗

Parallelized convolutional interleaver implementation for efficient DDR memory access

Convolutional interleavers are used in many different communications systems to correct for burst errors due to atmospheric fades and scintillation. The interleaver size is related to the channel coherence time and the data rate. Small convolutional interleavers can be implemented in a field programmable gate array (FPGA) block random access memory (BRAM). However, large interleavers exceeding the size of the BRAM on the FPGA are necessary for channels with longer fades and higher data rates. Therefore, an implementation utilizing double data rate (DDR) memory external to the FPGA is necessary. Wide DDR memory data buses can make the use of DDR memory for convolutional interleavers inefficient when individual symbols are written to and read from the memory. DDR memory operational speeds can also limit the data rate of the interleaver. The Consultative Committee for Space Data Systems (CCSDS) Optical Communications High Photon Efficiency (HPE) standard utilizes a convolutional channel symbol interleaver. A previous implementation of the HPE standard utilized BRAM for the convolutional interleaver, but mission requirements for the upcoming Optical Artemis-2 Orion (O2O) communications demonstration dictate the use of an interleaver exceeding the size of the BRAM. An algorithm and method for implementing the convolutional interleaver in the FPGA with DDR memory is described in this paper.

Optical communications↗

Analyzing line-of-sight selection biases in galaxy-scale strong lensing with external convergence and shear

The upcoming Vera Rubin Observatory Legacy Survey of Space and Time (LSST) will dramatically increase the number of strong gravitational lensing systems, requiring precise modeling of line-of-sight (LOS) effects to mitigate biases in lensing observations and cosmological inferences. We develop a method to construct joint distributions of external convergence (κ ext ) and shear (γ ext ) for strong lensing LOS by aggregating large-scale structure simulations with high-resolution halo renderings and non-linear correction. Our approach captures both smooth background matter and perturbations from halos, enabling accurate modeling of LOS effects. Here, we apply non-linear LOS corrections to κ ext and γ ext that address the non-additive lensing effects caused by objects along the LOS in strong lensing. We find that, with a minimum image separation of 1.0'', non-linear LOS correction due to the presence of a dominant deflector slightly increases the ratio of quadruple to double lenses; this non-linear LOS correction also introduces systematic biases of ∼ 0.1% for galaxy-AGN lens in the inferred Hubble constant (H 0 ) if not accounted for. We also observe a 0.66% bias for galaxy-galaxy lenses on H 0 , and even larger biases 1.02% for galaxy-AGN systems if LOS effects are not accounted for. These results highlight the importance of LOS for precision cosmology. The publicly available code and datasets provide tools for incorporating LOS effects in future analyses.

Hubble constant↗

Li interaction-induced phase transition from black to blue phosphorene

A comprehensive first-principle calculation has been carried out and revealed that at sufficiently high Li concentration and certain well-defined configurations a phase transition from black to blue phosphorene can take place. Blue phosphorene, a newly predicted allotrope of phosphorus, possesses unique crystalline and electronic structure and is a promising candidate, not only for fundamental research but also for electronic and optoelectronic applications. Methods to growth high quality blue phosphorene layers are highly desirable but challenging. Here, a novel kinetic pathway to grow blue phosphorene layers from black phosphorene layers via Li intercalation is proposed based on first principle study. This study pointed out that Li atoms intercalated in black phosphorene could act as ‘catalyst’ in the ‘reactive region’ of the lone pair of P atoms, leading to a P-P bond breaking and subsequently, a local structural transformation from orthorhombic lattice to an assembly of parallel narrow nanoribbons with rhombohedra-like symmetry. During Li deintercalation, these nanoribbons are self-mended and form blue phosphorene layers. The interlayer distance was found 4.60 Å for double layer with AA stacking and 4.13 Å for multilayer with ABC stacking, respectively, indicating a monolayer blue phosphorene can be mechanically exfoliated. Furthermore, this study also points out the possibility of new phases in other systems, where intercalation can lead to an unexpected structural phase transition and even a discovery of novel materials.

36 MATERIALS SCIENCE↗

Mosaic Cu I –Cu II –In III 2D Perovskites: Pressure–Dependence of the Intervalence Charge Transfer and a Mechanochemical Alloying Method

The perovskite (BA) 4 [Cu II (Cu I In III ) 0.5 ]Cl 8 (1 BA ; BA + =butylammonium) allows us to study the high-pressure structural, optical, and transport properties of a mixed-valence 2D perovskite. Compressing 1 BA reduces the onset energy of Cu I/II intervalence charge transfer from 1.2 eV at ambient pressure to 0.2 eV at 21 GPa. The electronic conductivity of 1 BA increases by 4 orders of magnitude upon compression to 20 GPa, when the activation energy for conduction decreases to 0.16 eV. In contrast, Cu II perovskites achieve similar conductivity at ≈50 GPa. The solution-state synthesis of these perovskites is complicated, with more undesirable side products likely from the precursor mixtures containing three different metal ions. Finally, to circumvent this problem, we demonstrate an efficient mechanochemical synthesis to expand this family of halide perovskites with complex composition by simply pulverizing together powders of 2D Cu II single perovskites and Cu I In III double perovskites.

2D perovskite↗

Fatigue analysis of the Spallation Neutron Source 2 MW target design

Upgrades to the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory are under way with two major projects. The first project is the Proton Power Upgrade (PPU), which will double the power capacity of the SNS accelerator system to enable the operation of a future second neutron source target station—the second project. PPU also will increase power to the SNS first target station – which currently operates at 1.4 MW with 1.0 GeV protons – to 2 MW with 1.3 GeV protons. Final design of the PPU 2 MW target module is finished, including all necessary design and analysis calculations. The fatigue evaluation described herein is an assessment of the fitness of the PPU 2 MW target mercury vessel to resist failure from cyclic loading from the pulsed 60 Hz proton beam and thermal changes from disrupted operation. In addition to the reliability predictions, the method, detail, and depth of this fatigue evaluation are superior to those of past target design assessments. Furthermore, the thermal fatigue life is predicted to exceed 3125 thermal cycles per 1250 h of operation for all load cases. The design also meets the (relative) fatigue design goal for combined thermal and pulse loading of greater than 0.5 times the minimum fatigue life calculated for a jet-flow target design operating at 1.4 MW—the most robust design to date in terms of resistance to fatigue failure. From the onset of the PPU, it has been known that pulse loading requires effective application of helium gas injection into the target mercury to reduce beam pressure loading. For the PPU 2 MW target, none of the pulse load cases requires a maximum strain reduction from gas injection of more than 50% (for base material) to meet the fatigue design goal. This level of reduction is achievable from gas injection, according to historical strain measurements from 1.4 MW target operation. Overall, the PPU 2 MW target design is predicted to have superior resistance to fatigue failure compared with past target designs.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗