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At least 883 records · Page 49

Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

More than 95% of silicate minerals and other oxides found in meteorites were melted, or vaporized and recondensed in the Solar Nebula prior to their incorporation into meteorite parent bodies. Gravitational accretion energy and heating via radioactive decay further transformed oxide minerals accreted into planetesimals. In such an oxygen-rich environment the carbonaceous dust that fell into the nebula as an intimate mixture with oxide grains should have been almost completely converted to CO. While some pre-collapse, molecular-cloud carbonaceous dust does survive, much in the same manner as do pre-solar oxide grains, such materials constitute only a few percent of meteoritic carbon and are clearly distinguished by elevated D/H, N-15/N-16, C-13/C-12 ratios or noble gas patterns. Carbonaceous Dust in Meteorites: We argue that nearly all of the carbon in meteorites was synthesized in the Solar Nebula from CO and that this CO was generated by the reaction of carbonaceous dust with solid oxides, water or OH. It is probable that some fraction of carbonaceous dust that is newly synthesized in the Solar Nebula is also converted back into CO by additional thermal processing. CO processing might occur on grains in the outer nebula through irradiation of CO-containing ice coatings or in the inner nebula via Fischer-Tropsch type (FTT) reactions on grain surfaces. Large-scale transport of both gaseous reaction products and dust from the inner nebula out to regions where comets formed would spread newly formed carbonaceous materials throughout the solar nebula. Formation of Organic Carbon: Carbon dust in the ISM might easily be described as inorganic graphite or amorphous carbon, with relatively low structural abundances of H, N, O and S . Products of FTT reactions or organics produced via irradiation of icy grains contain abundant aromatic and aliphatic hydrocarbons. aldehydes, keytones, acids, amines and amides.. The net result of the massive nebular carbon cycle is to convert relatively inert carbonaceous dust from the ISM into the vital organic precursors to life such as amino acids and sugars intimately mixed with dust and ice in primitive planetesimals. Since the number of carbon atoms entering the Solar Nebula as dust exceeds the number of atoms entering the nebula as oxide grains. the formation of large quantities of complex organic molecules may represent the largest single chemical cycle in the nebula.

Nuth, Joseph A., III↗

The Mars Environmental Compatibility Assessment MECA Abrasion Tool

The Mars Environmental Compatibility Assessment (MECA) experiment, an instrument suite to be flown on Mars Surveyor 2001, will include a tool for doing simple mineralogical scratch and streak tests on particles from the Martian regolith. The Abrasion Tool will be applied to particles that adhere to highly polished substrates of various hardnesses. Granular soil components will be subjected to a compressive force of about 3 N using a leaf spring. The spring will be applied with a paraffin actuator capable of a 0.76 mm throw to achieve a maximum displacement of about 7.5 mm at the tip of the tool. The pressure per grain will be dependent on the grain size, the number of grains that adhere to the substrate and the number of grains in compression. The pressure per particle is expected to be on the order of 100 MPa - 1 GPa. The MECA sample wheel containing the substrates will be rotated after the particles are placed in compression to produce scratches or pits. A primary goal of the Abrasion Tool is to identify quartz (Mohs' hardness = 7) using substrates of varying hardnesses. Quartz is considered hazardous to future human explorers of Mars because it can cause silicosis of the lungs if it is of respirable size. It is also hazardous to machinery, structures, and space suits because of its ability to abrade and scratch surfaces. Since large quantities of minerals harder than quartz are not expected, any scratches produced on polished quartz substrates might be reasonably attributed to quartz particles, although there may be minerals such as impact metamorphic diamond in the soils. Careful calibration of the tool will be necessary to ensure that grains are not overloaded; for example, a steel ball pressed into glass will produce a Hertzian fracture, even though it is softer than glass. Other minerals, such as magnetite (Mohs'hardness = 6.5) have been shown to scratch glass ceramics such as Zerodur (Mohs' hardness = 6.5). Thus, minerals can be differentiated: note that regardless of the mineral species, if any particle is harder than 6.5 it will certainly be an interesting discovery for both planetary geology and human exploration concerns. The scratches will be identified using the 6X optical microscope and profiled with the atomic force microscope included in the MECA instrument suite. Analysis of the scratch morphology will yield evidence concerning the shape of the particle responsible for producing each scratch. For example, angular grains should leave vertical cracks with microconchoidal lateral chipping, while rounded grains might leave chattermarks, or nested partial Hertzian cracks. Particle shape can thus be inferred from these indentation modes, as well as material hardness. In addition, particle size information may also be available if pits caused by rolling particles can be identified. Converse to scratching, the minerals may be crushed at their contact points, and be smeared onto the target substrates to leave what geologists refer to as "streaks". These are coldwelded trails of mineral material that have structure and color indicative of mineral composition. The AFM will determine the morphology of these streaks, while the microscope will ascertain the color. On the harder substrates, we might expect streaking to dominate; on the softer substrates, scratching may dominate. Progressions of material interactions across the substrate selection will be a valuable source of data for mineral discrimination. It should also be noted that many minerals have coatings (such as iron oxides), and these will have to be differentiated from the host mineral grains; laboratory tests will establish the effects of such coatings on the scratch results. Finally, we note that the microscope will provide corroborative data regarding likely mineral species by grain shapes, fracture patterns, surface textures, colr, and UV fluorescence reactions.

Kuhlman, K. R.↗

The Mars Environmental Compatibility Assessment (MECA) Abrasion Tool

The Mars Environmental Compatibility Assessment (MECA) experiment, an instrument suite to be flown on Mars Surveyor 2001, will include a tool for doing simple mineralogical scratch and streak tests on particles from the Martian regolith. The Abrasion Tool will be applied to particles that adhere themselves to highly polished substrates of various hardnesses. Granular soil components will be subjected to a compressive force of about 3 N using a leaf spring. The spring will be applied with a paraffin actuator capable of a 0.76 mm throw to achieve a maximum displacement of about 7.5 mm at the tip of the tool. The pressure per grain will be dependent on the grain size, the number of grains that adhere to the substrate and the number of grains in compression. The pressure per particle is expected to be on the order of 100 MPa - 1 GPa. The MECA sample wheel containing the substrates will be rotated after the particles are placed in compression to produce scratches or pits. A primary goal of the Abrasion Tool is to identify quartz (Mohs' hardness = 7) using substrates of varying hardnesses. Quartz is considered hazardous to future human explorers of Mars because it can cause silicosis of the lungs if it is of respirable size. It is also hazardous to machinery, structures, and space suits because of its ability to abrade and scratch surfaces. Since large quantities of minerals harder than quartz are not expected, any scratches produced on polished quartz substrates might be reasonably attributed to quartz particles, although there may be minerals such as impact metamorphic diamond in the soils. Careful calibration of the tool will be necessary to ensure that grains are not overloaded; for example, a steel ball pressed into glass will produce a Hertzian fracture, even though it is softer than glass. Other minerals, such as magnetite (Mohs' hardness = 6.5) have been shown to scratch glass ceramics such as Zerodur (Mohs' hardness = 6.5). Thus, minerals can be differentiated: note that regardless of the mineral species, if any particle is harder than 6.5 it will certainly be an interesting discovery for both planetary geology and human exploration concerns. The scratches will be identified using the 6X optical microscope and profiled with the atomic force microscope included in the MECA instrument suite. Analysis of the scratch morphology will yield evidence concerning the shape of the particle responsible for producing each scratch. For example, angular grains should leave vertical cracks with microconchoidal lateral chipping, while rounded grains might leave chatter marks, or nested partial Hertzian cracks. Particle shape can thus be inferred from these indentation modes, as well as material hardness. In addition, particle size information may also be available if pits caused by rolling particles can be identified. Converse to scratching, the minerals may be crushed at their contact points, and be smeared onto the target substrates to leave what geologists refer to as "streaks". These are cold-welded trails of mineral material that have structure and color indicative of mineral composition. The AFM will determine the morphology of these streaks, while the microscope will ascertain the color. On the harder substrates, we might expect streaking to dominate; on the softer substrates, scratching may dominate. Progressions of material interactions across the substrate selection will be a valuable source of data for mineral discrimination. It should also be noted that many minerals have coatings (such as iron oxides), and these will have to be differentiated from the host mineral grains; laboratory tests will establish the effects of such coatings on the scratch results. Finally, we note that the microscope will provide corroborative data regarding likely mineral species by grain shapes, fracture patterns, surface textures, color, and UV fluorescence reactions. Additional information is contained in the original extended abstract.

Kuhlman, K. R.↗

Determination of Gas-Phase Ion Structures of Locally Polar Homopolymers Through High-Resolution Ion Mobility Spectrometry–Mass Spectrometry

The strong synergy arising from coupling two orthogonal analytical techniques such as ion mobility and mass spectrometry can be used to separate complex mixtures and determine structural information of analytes in the gas phase. A tandem study is performed using two systems with different gases and pressures to ascertain gas-phase conformations of homopolymer ions. Aside from spherical and stretched configurations, intermediate configurations formed by a multiply charged globule and a “bead-on-a-string” appendix are confirmed for polyethylene-glycol (PEG), polycaprolactone (PCL), and polydimethylsiloxane (PDMS). These intermediate configurations are shown to be ubiquitous for all charge states and masses present. For each charge state, configurations evolve in two distinctive patterns: an inverse evolution which occurs as an elementary charge attached to the polymer leaves the larger globule and incorporates itself into the appendage, and a forward evolution which reduces the globule without relinquishing a charge while leaving the appendix relatively constant. Forward evolutions are confirmed to form self-similar family shapes that transcend charge states for all polymers. Identical structural changes occur at the same mass over charge regardless of the system, gas or pressure strongly suggesting that conformations are only contingent on number of charges and chain length, and start arranging once the ion is at least partially ejected from the droplet, supporting a charge extrusion mechanism. Configurational changes are smoother for PDMS which is attributed to the larger steric hindrance caused by protruding pendant groups. This study has implications in the study of the configurational space of more complex homopolymers and heteropolymers. .

74 ATOMIC AND MOLECULAR PHYSICS↗

Formation of Carbon Dioxide Attached Fragment Ions in the Fragmentation of Deprotonated Tolfenpyrad and Tebufenpyrad

The in-source collision-induced dissociation (CID) and MS/MS mass spectra of deprotonated tolfenpyrad and tebufenpyrad both showed an unusual fragment ion at m/z 187, but its fragmentation pattern and structure could not be explained by logical neutral losses. Accurate mass measurement indicated that the mass difference between this fragment ion and the dominant fragment ion at m/z 143 equaled to a carbon dioxide (CO{sub 2}) molecule. The isolation of the fragment ion m/z 143 in the mass analyzer could spontaneously give rise to the ion m/z 187. The Gibbs free energy of carbon dioxide addition to deprotonated pyrazole ion was significantly negative from the computational results. According to these results, we derived a proposal for the formation and structure of the ion m/z 187, which was an attachment of molecular carbon dioxide to the fragment ion m/z 143 to produce a carboxylate anion. The trace carbon dioxide was speculated to be derived from the residual atmosphere or collision gas in the instrument. This study is valuable for the qualitative and quantitative mass spectrometry analysis of pesticides containing the pyrazole functional group. .

74 ATOMIC AND MOLECULAR PHYSICS↗

Simulations for x-ray imaging of wave-packet dynamics

Previous work on imaging wave-packet dynamics with x-ray scattering revealed that the scattering patterns deviate substantially from the notion of instantaneous momentum density of the wave packet. Here we show that scattering patterns can provide clear insights into the electron wave-packet dynamics if the final state of the scattered electron and the scattered photon momentum are determined simultaneously. The scattering probability is shown to be proportional to the modulus square of the Fourier transform of the instantaneous electronic spatial wave function weighted by the final state of the electron. Several cases for the choice of final state of the electron are explored. First, the case where the final state can be measured up to a given principal quantum number n and orbital angular momentum l are presented. Next, the case where the final states can only be determined up to a given energy is discussed. Lastly, the case of an initial wave packet consisting of a large amount of a known stationary state and a small amount of an unknown stationary state is examined. The scattering profile is used to determine the properties of the unknown state in the wave packet.

74 ATOMIC AND MOLECULAR PHYSICS↗

The 1.66 μm spectrum of the ethynyl radical, CCH

Frequency-modulated diode laser transient absorption spectra of the ethynyl radical have been recorded at wavelengths close to 1.66 μm. The observed spectrum includes strong, regular, line patterns. The two main bands observed originate in the ground $\tilde{χ}$ 2 Σ + state and its first excited bending vibrational level of 2 $Π$ symmetry. The upper states, of 2 Σ + symmetry at 6055.6 cm -1 and 2 $Π$ symmetry at 6413.5 cm -1 , respectively, had not previously been observed and the data were analyzed in terms of an effective Hamiltonian representing their rotational and fine structure levels to derive parameters which can be used to calculate rotational levels up to J = 37/2 for the 2 $Π$ level and J = 29/2 for the 2 Σ one. Additionally, a weaker series of lines have been assigned to absorption from the second excited bending, (0 2 0), level of 2 Σ symmetry, to a previously observed state of 2 $Π$ symmetry near 6819 cm -1 . These strong absorption bands at convenient near-IR laser wavelengths will be useful for monitoring CCH radicals in chemical systems.

74 ATOMIC AND MOLECULAR PHYSICS↗

A DNA molecular printer capable of programmable positioning and patterning in two dimensions

Nanoscale manipulation and patterning usually require costly and sensitive top-down techniques such as those used in scanning probe microscopies or in semiconductor lithography. DNA nanotechnology enables exploration of bottom-up fabrication and has previously been used to design self-assembling components capable of linear and rotary motion. In this work, we combine three independently controllable DNA origami linear actuators to create a nanoscale robotic printer. The two-axis positioning mechanism comprises a moveable gantry, running on parallel rails, threading a mobile sleeve. We show that the device is capable of reversibly positioning a write head over a canvas through the addition of signaling oligonucleotides. We demonstrate “write” functionality by using the head to catalyze a local DNA strand–exchange reaction, selectively modifying pixels on a canvas. Furthermore, this work demonstrates the power of DNA nanotechnology for creating nanoscale robotic components and could find application in surface manufacturing, biophysical studies, and templated chemistry.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Classify QCD phase transition with deep learning

The state-of-the-art pattern recognition method in machine learning (deep convolution neural network) is used to identify the equation of state (EoS) employed in the relativistic hydrodynamic simulations of heavy ion collisions. High-level correlations of particle spectra in transverse momentum and azimuthal angle learned by the network act as an effective EoS-meter in deciphering the nature of the phase transition in QCD. The EoS-meter is model independent and insensitive to other simulation inputs including the initial conditions and shear viscosity for hydrodynamic simulations. Through this study we demonstrate that there is a traceable encoder of the dynamical information from the phase structure that survives the evolution and exists in the final snapshot of heavy ion collisions and one can exclusively and effectively decode these information from the highly complex final output with machine learning when traditional methods fail. Besides the deep neural network, the performance of traditional machine learning classifiers are also provided.

74 ATOMIC AND MOLECULAR PHYSICS↗

Simulation and Emulation of X-Ray Diffraction from Dynamic Compression Experiments

Many important aspects of the dynamic thermo-mechanical response of materials occur at the mesoscale, i.e. a physical scale of interactions smaller than what can be adequately described by homogenous behaviors, yet larger than the scale of the atomic lattice. Concurrent advancements in computational power, continuum theory, and experimental diagnostics are enabling unprecedented understanding of such interactions. However, we cannot develop a sufficient level of confidence in such mesoscale capability until the constitutive description of the underlying constituents is reliably representative of their actual physical behavior. Therefore, there is a strong need to combine experimental, modeling, and data-science techniques to validate models of the thermomechanical response of individual single crystals. One experimental diagnostic with high potential impact to shock physics and materials science is in-situ x-ray diffraction. This paper is primarily focused on simulation of x-ray diffraction in shock physics, but with an aim toward quantifying parametric uncertainty of simulation models. Here, we develop and demonstrate a data-science and model-driven approach to constrain the parameterization of continuum models of crystal lattice deformation associated with the shock response of crystalline materials. The framework is built around the connection between continuum hydrodynamic simulations of lattice deformation and a new Bragg diffraction simulation code, BarberShop. The dynamic deformation of a crystal lattice is modeled using the DiscoFlux model within an arbitrary Lagrangian-Eulerian hydrodynamic code, FLAG. These detailed continuum simulations of lattice deformation can be computationally slow, thus a statistical model is used to emulate the evolution of lattice deformation fields in time and across the considered model parameter space. Emulated lattice deformation fields can then be generated rapidly for any combination of physics model parameters. In turn, these fields can be fed into BarberShop to realize a rapid prediction of Bragg diffraction patterns associated with particular values of physics model parameters. The framework enables parameterization of the single crystal model to obtain Bragg diffraction patterns that most closely resemble a corresponding measurement. Furthermore, the framework naturally provides sensitivities of the lattice deformation to the physics parameters. We highlight the utility of this framework through the application to a synthetic closed-loop inverse problem leading to the parameterization of a single crystal material model. As a model problem, we consider the dynamic response of the energetic molecular crystal, cyclotrimethylenetrinitramine (or RDX), under dynamic compression induced by simulated flyer plate impact experiments.

36 MATERIALS SCIENCE↗

Prediction of low-Z collinear and noncollinear antiferromagnetic compounds having momentum-dependent spin splitting even without spin-orbit coupling

The over 60 years old Rashba-Dresselhaus effect predicts spin-orbit coupling (SOC) induced momentum-dependent spin splitting and spin polarization in materials with noncentrosymmetric structures. Strong SOC induced effects usually require high-atomic number (Z) elements such as rare-earth elements. It has recently been pointed out that antiferromagnets could hold SOC-independent spin splitting and spin polarization. In the present work we develop the spatial and magnetic symmetry conditions enabling such antiferromagnet (AFM)-induced spin splitting, dividing the 1651 magnetic space groups into seven different spin splitting prototypes (SST-1 to SST-7). This analysis places the physics of AFM spin splitting (SST-4) within the broader context of symmetry conditions that enable the more familiar forms of spin splitting, such as ferromagnetic Zeeman effect (SST-5), nonmagnetic no spin splitting (SST-6), and the nonmagnetic Rashba and Dresselhaus effects (SST-7). The AFM-induced spin splitting and spin polarization do not necessarily require breaking of inversion symmetry or the presence of SOC, hence can exist even in centrosymmetric, low-Z light element compounds, considerably broadening the material base for spin manipulations. We use the “inverse design” approach of first formulating the target property (here, spin splitting in low-Z compounds not restricted to low symmetry structures), then derive the enabling physical design principles—the magnetic symmetry conditions—to search realizable compounds that satisfy these a priori design principles. This process uncovers 422 magnetic space groups (160 centrosymmetric and 262 noncentrosymmetric) that could hold AFM-induced, SOC-independent spin splitting and spin polarization. We then search for stable compounds following such enabling symmetries. We investigate the electronic and spin structures of some selected prototype compounds by density functional theory (DFT) and find spin textures that are different than the traditional Rashba-Dresselhaus patterns and exist even in the absence of SOC effect. We provide the DFT results for all antiferromagnetic spin splitting prototypes (SST-1, SST-2, SST-3, SST-4), and concentrate on two limits of SST-4 that are particularly unusual: When spin splitting is momentum dependent (just like the Rashba effect) but is enabled in antiferromagnets even in the absence of SOC in the Hamiltonian. This includes examples of (a) centrosymmetric SST-4A compounds (e.g., orthorhombic LaMnO 3 illustrating collinear AFM, as well as cubic NiS 2 illustrating noncollinear AFM) and (b) noncentrosymmetric SST-4B compounds (e.g., rhombohedral MnTiO 3 illustrating collinear AFM and hexagonal ScMnO 3 illustrating noncollinear AFM). The symmetry design principles outlined here, along with their transformation into an inverse design material search approach and DFT verification, could open the way to their experimental examination.

36 MATERIALS SCIENCE↗

Integrated modeling of boron powder injection for real-time plasma-facing component conditioning

An integrated modeling framework for investigating the application of solid boron (B) powder injection for real-time surface conditioning of plasma-facing components (PFCs) in tokamak environments is presented. Utilizing the DIII-D impurity powder dropper (IPD) setup, this study simulates B powder injection scenarios ranging from milligrams to tens of milligrams per second, corresponding to boron flux rates of 10 20 –10 21 B/s in standard L-mode conditions. The comprehensive modeling approach combines EMC3-EIRENE for simulating the deuterium plasma background and the Dust Injection Simulator (DIS) for the ablation and transport of the boron powder particles. EMC3 trace impurity fluid modeling results show substantial boron transport to the inboard lower divertor, predominantly influenced by the main ion plasma flow. The dependency on powder particle size (5-250 µm) was found to be insignificant for the scenario considered. The effects of erosion and redeposition were considered to reconcile the discrepancies with experimental observations, which saw substantial deposition on the outer divertor plasma-facing components. For this purpose, the WallDYN3D code was updated to include boron sources within the plasma domain and integrated into the modeling framework. The mixed-material migration modeling shows evolving boron deposition patterns, suggesting the formation of mixed B-C layers or predominantly B coverage depending on the powder mass flow rate. While the modeling outcomes at lower B injection rates tend to align with DIII-D experimental observations, the prediction of near-pure boron layers at higher rates has yet to be experimentally verified in the carbon environment of the DIII-D tokamak. The extensive reach of boron layers found in the modeling suggests the need for modeling that encompasses the entire wall geometry for more accurate experimental correlations. This integrated approach sets a precedent for analyzing and applying real-time in-situ boron coating techniques in advanced tokamak scenarios, potentially extendable to ITER.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Physical properties of intergrowth compound Eu 2 CuZn 2 P 3

Here, the physical properties of single-crystalline Eu 2 ⁢CuZn 2 ⁢P 3 were inspected via thermodynamic, transport, and neutron diffraction measurements. Eu 2 ⁢ CuZn 2⁢ P 3 is composed of EuCuP and EuZn 2 ⁢ P 2 motifs stacked in a one-to-one ratio. The magnetic response of Eu 2 ⁢ CuZn 2 ⁢ P 3 is similar to that of EuZn 2 ⁢ P 2 in its A-type antiferromagnetic (semiconducting) state. A Néel temperature of T N = 40.3K is obtained from the specific heat capacity. Single-crystal neutron diffraction reveals a (001) magnetic propagation vector, with primarily in-plane moments coupled along [001] in an up-up-down-down pattern. This spin structure retains the ferromagnetic EuCuP motifs and antiferromagnetic coupling across the EuZn 2 ⁢P 2 motifs. The electrical resistivity is characterized by metallic behavior above 100 K, an increase in ρ upon cooling below ≈ 75K, and a large negative magnetoresistance below T N . First principles calculations evidence a narrow band gap for antiferromagnetic ordering and semimetallic behavior for the ferromagnetic state. This is consistent with the observed effect of magnetic field on the electrical resistivity. Hall effect measurements reveal a field-induced, negative anomalous Hall effect that increases on cooling down to 2 K. Also, an unconventional contribution to the Hall effect dominates the low-field Hall signal, particularly near T N , and is similar in appearance to a topological Hall effect. However, further work is necessary to understand if any of the transport properties have topological origins or if magnetism-induced modifications to the Fermi surface induce these unusual Hall effect signals in this and related materials.

36 MATERIALS SCIENCE↗

Resistivity of Carbon-Carbon Composites Halved

Carbon-carbon composites have become the material of choice for applications requiring strength and stiffness at very high temperatures (above 2000 C). These composites comprise carbon or graphite fibers embedded in a carbonized or graphitized matrix. In some applications, such as shielding sensitive electronics in very high temperature environments, the performance of these materials would be improved by lowering their electrical resistivity. One method to lower the resistivity of the composites is to lower the resistivity of the graphite fibers, and a proven method to accomplish that is intercalation. Intercalation is the insertion of guest atoms or molecules into a host lattice. In this study the host fibers were highly graphitic pitch-based graphite fibers, or vapor-grown carbon fibers (VGCF), and the intercalate was bromine. Intercalation compounds of graphite are generally thought of as being only metastable, but it has been shown that the residual bromine graphite fiber intercalation compound is remarkably stable, resisting decomposition even at temperatures at least as high as 1000 C. The focus of this work was to fabricate composite preforms, determine whether the fibers they were made from were still intercalated with bromine after processing, and determine the effect on composite resistivity. It was not expected that the resistivity would be lowered as dramatically as with graphite polymer composites because the matrix itself would be much more conductive, but it was hoped that the gains would be substantial enough to warrant its use in high-performance applications. In a collaborative effort supporting a Space Act Agreement between the NASA Glenn Research Center and Applied Sciences, Inc. (Cedarville, OH), laminar preforms were fabricated with pristine and bromine-intercalated pitch-based fibers (P100 and P100-Br) and VGCF (Pyro I and Pyro I-Br). The green preforms were carbonized at 1000 C and then heat treated to 3000 C. To determine whether the fibers in the samples were still intercalated after composite fabrication, they were subjected to X-ray diffraction. The composites containing intercalated graphite fibers showed much higher background scatter than that of pristine fibers, indicating the presence of bromine in the samples. More importantly, faint features indicative of intercalation were visible in the diffraction pattern, showing that the fibers were still intercalated.

Gaier, James R.↗

Automated Construction of Potential Energy Surfaces Suitable to Describe van der Waals Complexes with Highly Excited Nascent Molecules: The Rotational Spectra of Ar–CS( v ) and Ar–SiS( v )

Some reactions produce extremely hot nascent products which nevertheless can form sufficiently long-lived van der Waals (vdW) complexes—with atoms or molecules from a bath gas—as to be observed via microwave spectroscopy. Theoretical calculations of such unbound resonance states can be much more challenging than ordinary bound-state calculations depending on the approach employed. One encounters not just the floppy, and perhaps multiwelled potential energy surface (PES) characteristic of vdWs complexes, but in addition, one must contend with excitation of the intramolecular modes and its corresponding influence on the PES. Straightforward computation of the (resonance) rovibrational levels of interest, involves the added complication of the unbound nature of the wave function, often treated with techniques such as introducing a complex absorbing potential. Here, we have demonstrated that a simplified approach of making a series of vibrationally effective PESs for the intermolecular coordinates—one for each reaction product vibrational quantum number of interest—can produce vdW levels for the complex with spectroscopic accuracy. This requires constructing a series of appropriately weighted lower-dimensional PESs for which we use our freely available PES-fitting code AUTOSURF. The applications of this study are the Ar–CS and Ar–SiS complexes, which are isovalent to Ar–CO and Ar–SiO, the latter of which we considered in a previously reported study. Using a series of vibrationally effective PESs, rovibrational levels and predicted microwave transition frequencies for both complexes were computed variationally. A series of shifting rotational transition frequencies were also computed as a function of the diatom vibrational quantum number. The predicted transitions were used to guide and inform an experimental effort to make complementary observations. Comparisons are given for the transitions that are within the range of the spectrometer and were successfully recorded. Calculations of the rovibrational level pattern agree to within 0.2% with experimental measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydration Mechanisms in Nanoparticle Interaction and Surface Energetics

Work on the project advanced molecular level understanding, prediction and control of nanoscale hydration in salt solutions under electric stimuli or ionic patterning. Permeation of nanoporous electrodes at preset voltage underlies the function of ultracapacitors. Transitory regulation of wetting in nanoporous media by electric field spans an array of applications in materials, energy storage, and separation sciences. The physically related modulation of nanoparticle solubility by surface charges can significantly extend the range of the nanomaterial applications, improve processing techniques, and potentially alleviate environmental concerns. Pore/solution equilibria, and activated kinetics of liquid gating by nanoconfined electrolytes are challenging problems at the forefront of experimental and theoretical research. Addressing these problems from a molecular perspective required the development of state-of-the-art simulation algorithms in statistical mechanics to capture complex processes in open systems under electric control. Parallel studies of wetting and dispersibility of polar and ionizing particles aim to uncover predictive relations between electrowetting, chemical functionalization, and geometry of nanomaterial particles. By nonequilibrium dynamic modeling, we elucidated electrolyte flow in nanochanels and associated electrokinetic energy conversion. Research on the program provided training opportunities for the next generation of scientists in computational chemistry. Insights, and methods from the project implicate broad segment of researchers in energy and nanosciences, materials and surface chemistry.

74 ATOMIC AND MOLECULAR PHYSICS↗

Trap-Assisted Dopant Compensation Prevents Shunting in poly-Si Passivating Interdigitated Back Contact Silicon Solar Cells

Interdigitated back contact (IBC) solar cells achieve the highest efficiencies of single-junction architectures, but complicated patterning of the rear fingers and spreading of dopants during processing inhibit their mainstream adoption due to concerns of shunting between the IBC fingers. One method of simplifying patterning at the rear is by using contact masks combined with plasma-enhanced chemical vapor deposition (PECVD) or ion implantation. However, the intrinsic isolation region becomes contaminated during high-temperature annealing by lateral diffusion of dopants and during masked PECVD by spreading of dopant radicals through region between the mask and the substrate. Despite this contamination, we show through scanning spreading resistance microscopy and Kelvin probe force microscopy that a ~20 µm wide compensating region exists with high enough resistivity to prevent shunting. We model this p-i-n poly-Si system using two simulation models: a simple resistor model considering only the capture of charge carriers by trap defects in poly-Si to reduce the conductivity, and a more refined 1-dimensional finite element model using Poisson’s equation, drift-diffusion equations, and recombination of carriers. Using this model, we show that high defect density significantly decreases the current across the region between the p- and n-type fingers, preventing shunting.

atom probe↗

An efficient computational framework for charge density estimation in twisted bilayer graphene

Electronic properties such as band structure and Fermi velocity in low-angle twisted bilayer graphene (TBG) are intrinsically dependent on the atomic structure. Rigid rotation between individual graphene layers provides an approximate description of the bilayer symmetry. Upon relaxation, in-plane displacement of the atoms in low angle TBG causes a change in the symmetry through the enlargement of the AB stacking regions and the reduction in size of AA and SP stacking regions. However, the effect of this in-plane relaxation on the charge density remains unexplored, because the necessary electronic structure calculations of such large supercells of low twist angle TBG are computationally infeasible. Therefore, we develop a computationally efficient framework that enables the exploration of the charge density symmetry of the low twist angle TBG. This framework is based on the Fourier representation of the charge density which presents high intensity Bragg peaks. Here we find that with the decrease of twist angle, low intensity satellite peaks also become apparent. Our framework incorporates these satellite peaks which reveals transformation of symmetry in the charge density distribution from high to low twist angle TBG. One striking outcome is the demonstration of the electron localization in the AA region of low twist angle TBG. Our framework helps to explain the effect of the atomistic relaxation on the charge density distribution and thus, it provides information about exotic electronic properties of low twist angle TBG at a low computational expense.

36 MATERIALS SCIENCE↗