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DOE OSTI2020

Multi-Scale Modeling Framework for Mercury Biogeochemistry

Multi-Scale modeling of mercury (Hg) geochemical speciation and reactions has been performed by integrating atomistic quantum chemical calculations with continuum scale speciation models. Major progress has been made in the improvement of quantum chemical models to calculate critical thermodynamic data for Hg complexes in aquatic environments. Rapid and reliable quantum chemical approaches have been developed for calculating acid dissociation constants (pK a ) and stability constants (log K), with calculated mean unsigned errors of 0.5 and 1.5 log units, respectively for ligand molecules and Hg complexes. At the continuum scale, systematic analysis of uncertainty propagation in mercury (Hg) speciation modeling has been conducted and was used to identify environmental conditions under which thermodynamic constant uncertainties are significant and recommended to be accounted for. The integrated framework for multi-scale modeling of mercury geochemistry is open to the research community through the web-based multiscale modeling aqueous speciation resource, AQUA-MER. The improved quantum chemical approaches for thermodynamic constant calculations are accessible through AQUA-MER and can be used to provide the missing constants in the continuum scale speciation calculations. In addition to low molecular mass Hg complex speciation, modeling natural aquatic environments also involve the transport of high molecular weight dissolved organic matter (DOM) in reactive flows simultaneously with equilibrium and kinetic reactions. To this end, atomistic MD simulations were performed to capture the details of aggregation, mechanisms and distribution of functional groups in DOM at the molecular level. The elemental composition and calculated bulk properties of the DOM models are in close agreement with experimental measurements. A travel-time based reactive transport model in the hyporheic zone of stream corridors was established for the multicomponent Hg-DOM-S system and implemented through PFLOTRAN.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

On the Prospect of Chemically Transferable Coarse-Grained Electronic Models for Soft Materials

Electronic coarse-graining (ECG) methods predict quantum-mechanical electronic properties directly from coarse-grained (CG) molecular configurations, enabling electronic predictions at mesoscale length scales. Here, we present a diagnostic assessment of the feasibility of chemically transferable ECG models across a broad polymer-relevant chemical space using all-atom, united-atom, and Martini-scale representations. While high-resolution ECG models achieve near-quantitative accuracy, we show that chemically transferable ECG at the Martini resolution fails because the CG force field does not sample the same configurational distribution of local molecular structure as that underlying the DFT-parameterized ECG model. We demonstrate that our proposed Element-Count-Label (ECL) representation, which augments Martini beads with explicit stoichiometric data, significantly improves chemical generalization across diverse polymer chemistries. However, we find that even with improved chemical resolution, the model cannot recover electronic property distributions that are absent from the configurational space sampled by the CG force field. These results demonstrate that chemically transferable ECG requires future Martini-like force fields to explicitly preserve quantum chemistry–compatible local molecular structure in addition to thermodynamic and structural fidelity.

Kidder, Katherine M [Department of Chemistry; Univ↗

DOE OSTI2021

Editorial: Quantum Information and Quantum Computing for Chemical Systems

Quantum computing has emerged as an exciting inter-disciplinary research topic that cuts across the traditional fields of physics, computer science, and engineering. It is a revolutionary model of computation that has offered new insights into methods for modeling and simulation of chemical systems. Applications of quantum computing to chemistry have demonstrated rapid progress on both theoretical and experimental fronts. Past theoretical efforts have shown how to adapt quantum computation to a variety of problems including electronic structure and molecular dynamics. In addition, the development of quantum algorithms for quantum chemistry has been stimulated by the greater availability of more capable quantum computing devices. Advances in the number and quality of qubits continues to enable remarkable proof-of-concept demonstrations working towards a milestone of quantum computational advantage.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2021

An Investigation into the Approximations Used in Wave Packet Molecular Dynamics for the Study of Warm Dense Matter

Wave packet molecular dynamics (WPMD) has recently received a lot of attention as a computationally fast tool with which to study dynamical processes in warm dense matter beyond the Born–Oppenheimer approximation. These techniques, typically, employ many approximations to achieve computational efficiency while implementing semi-empirical scaling parameters to retain accuracy. We investigated three of the main approximations ubiquitous to WPMD: a restricted basis set, approximations to exchange, and the lack of correlation. We examined each of these approximations in regard to atomic and molecular hydrogen in addition to a dense hydrogen plasma. We found that the biggest improvement to WPMD comes from combining a two-Gaussian basis with a semi-empirical correction based on the valence-bond wave function. A single parameter scales this correction to match experimental pressures of dense hydrogen. Ultimately, we found that semi-empirical scaling parameters are necessary to correct for the main approximations in WPMD. However, reducing the scaling parameters for more ab-initio terms gives more accurate results and displays the underlying physics more readily.

Angermeier, William A. (ORCID:0000000177161564)↗

NASA NTRS1972

Nonuniform concentration - A mechanism for drag reduction.

A large reduction in drag coefficient has been observed in certain external flows of aqueous solutions with high molecular weight polymer additives. A change in the near wake configuration is phenomenologically responsible for the drag reduction, but the underlying mechanism is presently unknown. An analogy to known phenomena in particulate suspensions is drawn which suggests nonuniform concentration of the polymer additive as an explanation. An analysis of the boundary layer on a sphere with varying viscosity was made to investigate the effect. The results indicate early transition to turbulence for concentration variations whose length scale is small compared with the momentum boundary layer thickness. Stabilization and delayed transition are indicated for thicker concentration layers. Observations are suggested for the thin concentration layers.

Rivard, W. C.↗

NASA NTRS1985

Tribological systems as applied to aircraft engines

Tribological systems as applied to aircraft are reviewed. The importance of understanding the fundamental concepts involved in such systems is discussed. Basic properties of materials which can be related to adhesion, friction and wear are presented and correlated with tribology. Surface processes including deposition and treatment are addressed in relation to their present and future application to aircraft components such as bearings, gears and seals. Lubrication of components with both liquids and solids is discussed. Advances in both new liquid molecular structures and additives for those structures are reviewed and related to the needs of advanced engines. Solids and polymer composites are suggested for increasing use and ceramic coatings containing fluoride compounds are offered for the extreme temperatures encountered in such components as advanced bearings and seals.

Buckley, D. H.↗

NASA NTRS1985

CO 4.6 micron emission lines from the IRC +10216 inner envelope

Results are presented of an investigation of gas in the inner envelope of IRC +10216 at a scale size (approximately 2 arcsec) never observed previously. Observations were made at the 4.6-micrometer fundamental vibration-rotation band of CO, employing an annular observing aperture to isolate radiation resonantly scattered from the extended molecular envelope. In addition to the expected emission up to the expansion velocity of the envelope, both CO and 13CO show evidence of high-velocity features in the blue wing of the line, beyond the 15 km/s expansion velocity. A mass loss rate for the inner envelope of approximately 5-7 x 10 to the -5 solar mass per year is derived (lower than the values derived for the extended envelope from millimeter CO data).

Sahai, R.↗

NASA NTRS1989

A multi-temperature TVD algorithm for relaxing hypersonic flows

In this paper, the extension of a multispecies TVD algorithm, second-order accurate for real-gas flows to a multitemperature formulation is described. The convection algorithm is coupled to internal relaxation processes, and the features of the coupling are examined. The first version consists of a three-temperature model, where translational-rotational, vibrational, and electronic energy modes are separately convected. Although several species are present, there is only one vibrational temperature in this model. The second version generalizes to a vibrational temperature for each molecular specie, with additional couplings between species. The algorithms are applied to a generic two-dimensional flow field, and results are compared with experimental observations.

Cambier, Jean-Luc↗

NASA NTRS1992

Simulation studies for surfaces and materials strength

Investigations were carried out in two major areas during the last reporting period. Energy- and structure-related properties of small gold clusters deposited on the GaAs(110) surface were investigated using a molecular dynamics procedure. Additionally, a comparative study of the many-body potentials of silicon systems was performed.

Halicioglu, Timur↗

NASA NTRS1992

Melt flow properties of LARC-TPI 1500 series mixtures

This study examines the melt-flow properties of 50/50 mixtures of high flow grade/medium flow grade LARC-TPI 1500 series pellets and a new form (94/6), of medium flow grade material which contains 6 percent of a low molecular weight imide additive. The flow properties are compared with previously reported flow properties of mixtures of earlier batches of high and medium flow grade TPI 1500 materials. Unlike the earlier batches of materials, the later materials were synthesized and mixed at Mitsui Toatsu Chemicals, Inc., Japan, and made into pellets before NASA received them for characterization. They exhibited a lower melt viscosity as well as improved melt stability.

Burks, H. D.↗

NASA NTRS2000

The Rotational Spectra of IO X(sub 1) (sup 2)pi(sub 3/2), v <= 13 and X(sub 2) (sup 2)pi(sub 1/2), v <= 9

The rotational spectra of IO in vibrational states up to v = 13 in the X(sub 1) (sup 2)pi(sub 3/2) state and up to v = 9 in the X2 (sup 2)pi(sub 1/2) state have been observed in an O2 discharge over molecular I2. In addition, I(18)O has been observed for both the X(sub 1) and X(sub 2) states up to v = 5. All data have been analyzed simultaneously with fixed isotopic ratios among the constants. This extends the data set for the X(sub 1) state described last year at this meeting and provides the first high resolution data for the X(sub 2) state and for I(18)O. An extensive set of parameters has been derived. These will be interpreted in terms of the electronic structure and the interatomic potential.

Miller, Charles E.↗

NASA NTRS2004

The Companion to the Central Mira Star of the Protoplanetary Nebula OH 231.8+4.2

We present deep optical long-slit spectra of the peculiar protoplanetary nebula (PPN) OH 231.8+4.2 obtained with the 6.5 m Baade Telescope at Las Campanas Observatory (Chile). In addition to the molecular absorption bands characteristic of the M9-10 III star inside OH 231.8+4.2 (QX Pup), we identify lines of the Balmer series in absorption, which do not form in the cool atmospheres of late M-type stars. We also confirm the presence of a blue continuum excess with an intensity that is a factor 30 larger than that expected for an M9-10 III star. Our results indicate the presence of a source hotter than QX Pup illuminating OH 231.8+4.2 that is likely a main-sequence star with spectral type A. We discuss how the formation and nebular evolution of OH 231.8+4.2 could have been affected by the presence of a binary system in its core.

binaries↗

NASA NTRS2012

Negative Ion Chemistry in the Coma of Comet 1P/Halley

Negative ions (anions) were identified in the coma of comet 1P/Halley from in-situ measurements performed by the Giotto spacecraft in 1986. These anions were detected with masses in the range 7-110 amu, but with insufficient mass resolution to permit unambiguous identification. We present details of a new chemical-hydrodynamic model for the coma of comet Halley that includes - for the first time - atomic and molecular anions, in addition to a comprehensive hydrocarbon chemistry. Anion number densities arc calculated as a function of radius in the coma, and compared with the Giotto results. Important anion production mechanisms arc found to include radiative electron attachment, polar photodissociation, dissociative electron attachment, and proton transfer. The polyyne anions C4H(-) and C6H(-) arc found to be likely candidates to explain the Giotto anion mass spectrum in the range 49-73 amu. Thc CN(-) anion probably makes a significant contribution to the mass spectrum at 26 amu. Larger carbon-chain anions such as C8H(1) can explain the peak near 100 amu provided there is a source of large carbon-chain-bearing molecules from the cometary nucleus.

Cordiner, M. A.↗

DOE OSTI2022

Characterization of the Interfacial Orientation and Molecular Conformation in a Glass-Forming Organic Semiconductor

The ability to control structure in molecular glasses has enabled them to play a key role in modern technology; in particular, they are ubiquitous in organic light-emitting diodes. While the interplay between bulk structure and optoelectronic properties has been extensively investigated, few studies have examined molecular orientation near buried interfaces despite its critical role in emergent functionality. Direct, quantitative measurements of buried molecular orientation are inherently challenging, and many methods are insensitive to orientation in amorphous soft matter or lack the necessary spatial resolution. To overcome these challenges, we use polarized resonant soft X-ray reflectivity (pRSoXR) to measure nanometer-resolved, molecular orientation depth profiles of vapor-deposited thin films of an organic semiconductor Tris(4-carbazoyl-9-ylphenyl)amine (TCTA). Our depth profiling approach characterizes the vertical distribution of molecular orientation and reveals that molecules near the inorganic substrate and free surface have a different, nearly isotropic orientation compared to those of the anisotropic bulk. Comparison of pRSoXR results with near-edge X-ray absorption fine structure spectroscopy and optical spectroscopies reveals that TCTA molecules away from the interfaces are predominantly planar, which may contribute to their attractive charge transport qualities. Buried interfaces are further investigated in a TCTA bilayer (each layer deposited under separate conditions resulting in different orientations) in which we find a narrow interface between orientationally distinct layers extending across ≈1 nm. Coupling this result with molecular dynamics simulations provides additional insight into the formation of interfacial structure. This study characterizes the local molecular orientation at various types of buried interfaces in vapor-deposited glasses and provides a foundation for future studies to develop critical structure–function relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2000

Molecular View of Protein Crystal Growth: Molecular Interactions, Surface Reconstruction and Growth Mechanism

Studies of the growth and molecular packing of tetragonal lysozyme crystals suggest that there is an underlying molecular growth mechanism, in addition to the classical one involving screw dislocation/2D) nucleation growth. These crystals are constructed by strongly bonded molecular chains forming helices about the 43 axes. The helices are connected to each other by weaker bonds. Crystal growth proceeds by the formation of these 4(sub 3) helices, which would explain some unexpected observations by earlier investigators, such as bimolecular growth steps on the (110) face. Another consequence of these molecular considerations is that only one of two possible packing arrangements could occur on the crystal faces and that their growth unit was at least a tetramer corresponding to the 4(sub 3) helix. Two new high resolution atomic force microscopy (AFM) techniques were developed to directly confirm these predictions on tetragonal lysozyme crystals. Most earlier investigations of protein crystal growth with AFM were in the low resolution mode which is adequate to investigate the classical growth mechanisms, but cannot resolve molecular features and mechanisms. Employing the first of the newly developed techniques, high resolution AFM images of the (110) face were compared with the theoretically constructed images for the two possible packing arrangements on this face. The prediction that the molecular packing arrangement of these faces corresponded to that for complete 4(sub 3) helices was confirmed in this manner. This investigation also showed the occurrence of surface reconstruction on protein crystals. The molecules on the surface of the (110) face were found to pack closer along the 4(sub 3) axes than those in the interior. The second new AFM technique was used to follow the growth process by measuring the dimensions of individual growth units on the (110) face. Linescans across a growth step, performed near the saturation limit of the crystals, allowed the growth unit dimensions to be measured as they were being incorporated into the crystal. These measurements showed that growth on the (110) face proceeded by the formation of new 4(sub 3) helices from the addition of many growth units of at least tetramer size. This is the first time that a time-resolved AFM technique has been used to observe individual molecular events during crystal growth.

Nadarajah, Arunan↗

DOE OSTI2020

Organic amendments change soil organic C structure and microbial community but not total organic matter on sub-decadal scales

Organic C has many benefits for soil, but it is depleted by tillage and crop harvest, and especially so for biofuel crops. Accordingly, strategies such as partially retaining stover or planting a cover crop can help ameliorate the negative effect of C removal. We used a long-term field experiment to study the impacts of stover retention and planting cover crop on soil organic matter (SOM), its extractable components and the soil microbial community. SOM chemical composition characterization was determined by electrospray ionization (ESI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sequential water, methanol (MeOH), and chloroform (CHCl3) extracts. The characteristics of the soil bacterial community were measured by phospholipid fatty acid (PLFA), real-time quantitative PCR, and 16S rRNA gene sequence. The variations in total SOM content, total microbial biomass, and bacterial population were slight among treatments, but SOM chemical compounds, arbuscular mycorrhizal fungi (AMF) biomass, and bacterial structure changed significantly, and especially so in the coupled application of stover retention and cover crop. Specifically, stover retention enriched more lignin-like compounds in soil, whereas cover crop enriched more condensed hydrocarbons, and had more compounds with an aromaticity index (AI) >0.5. The bacterial community was not altered by the cover crop, but the corn stover retention increased the relative abundances of Myxococcales (Deltaproteobacteria) and decreased that of Actinobacteria. Redundancy analysis (RDA) further unveiled that the bacterial community in the stover treatments had significantly positive association with CHCl3-extracted chemical classes, i.e. unsaturated hydrocarbon and lipid with the coupled application (stover and cover crop), and lignin and protein with the single corn stover treatment. Taken together, our study shows how different C addition practices influence the molecular composition of SOM and the structure of soil microbial communities.

Xu, Jiangbin↗

NASA NTRS1988

Additives Improve Processing Of Polyimides

Melt-processable polyimides maintain desirable polymer properties prepared by adding small amounts of certain low-molecular-weight, thermally stable additives. Useful in preparing void-free polyimide composites from higher flow resins that wet out fibers at lower processing temperatures. Applied to preparing high-temperature polyimide adhesives allowing enhanced wetting of adherends and ultimately better adhesion. Improvement to processing polyimides and potential application for production of films, coatings, adhesives, and composites.

St. Clair, Terry L.↗

DOE OSTI2023

Unveiling the Role of Compositional Drifts on the Tack of Pressure‐Sensitive‐Adhesives

Abstract Pressure‐sensitive‐adhesives (PSAs) are pervasive in electronic, automobile, packaging, and biomedical applications due to their ability to stick to numerous surfaces without undergoing chemical reactions. These materials are typically synthesized by the free radical copolymerization of alkyl acrylates and acrylic acid, leading to an ensemble of polymer chains with varying composition and molecular weight. Here, reversible addition−fragmentation chain‐transfer (RAFT) copolymerizations in a semi‐batch reactor are used to tailor the molecular architecture and bulk mechanical properties of acrylic copolymers. In the absence of cross‐links, the localization of acrylic acid toward the chain ends leads to microphase separation, creep resistance, and enhanced tack. However, in the presence of Al(acac) 3 crosslinker, the creep resistance remains unchanged and mostly the large‐strain mechanical properties are affected. This behavior is attributed to microphase separation, but also to a change in the energy required to break physical associations, and untangle and elongate associative polymers to large deformations.

Polymer Science↗