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At least 73 records · Page 4

Combining High-Throughput Experiments and Active Learning to Characterize Deep Eutectic Solvents

The high tunability of deep eutectic solvents (DESs) stems from the ease of changing their precursors and relative compositions. However, measuring the physicochemical properties across large composition and temperature ranges, necessary to properly design target-specific DESs, is tedious and error-prone and represents a bottleneck in the advancement and scalability of DES-based applications. As such, active learning (AL) methodologies based on Gaussian processes (GPs) were developed in this work to minimize the experimental effort necessary to characterize DESs. Owing to its importance for large-scale applications, the reduction of DES viscosity through the addition of a low-molecular-weight solvent was explored as a case study. A high-throughput experimental screening was initially performed on nine different ternary DESs. Then, GPs were successfully trained to predict DES viscosity from its composition and temperature, showcasing the ability of these stochastic, nonparametric models to accurately describe the physicochemical properties of complex mixtures. Finally, the ability of GPs to provide estimates of their own uncertainty was leveraged through an AL framework to minimize the number of data points necessary to obtain accurate viscosity modes. This led to a significant reduction in data requirements, with many systems requiring only five independent viscosity data points to be properly described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical Characterization of the NNO...O3 and NNO...O Complexes

The bonding mechanisms and bond strengths of complexes between two molecular and/or atomic species will be discussed. The implications of complex formation for stratospheric chemistry will be presented. Results of theoretical calculations on NNO ... O3 and NNO ...O will be used as specific examples to illustrate the principles of complex formation. The equilibrium structures and binding energies of these complexes will be presented as well as shifts in other molecular properties due to complexation, such as vibrational frequencies. Thermal dissociation rates will be presented. The theoretical methodology used in this study consists of high-level coupled-cluster calculations and more approximate density functional theory approaches, together with large one-particle basis sets.

Lee, Timothy J.↗

Organic chemistry on Titan

Features taken from various models of Titan's atmosphere are combined in a working composite model that provides environmental constraints within which different pathways for organic chemical synthesis are determined. Experimental results and theoretical modeling suggest that the organic chemistry of the satellite is dominated by two processes: photochemistry and energetic particle bombardment. Photochemical reactions of CH4 in the upper atmosphere can account for the presence of C2 hydrocarbons. Reactions initiated at various levels of the atmosphere by cosmic rays, Saturn 'wind', and solar wind particle bombardment of a CH4-N2 atmospheric mixture can account for the UV-visible absorbing stratospheric haze, the reddish appearance of the satellite, and some of the C2 hydrocarbons. In the lower atmosphere photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. It is concluded that the surface of Titan may contain ancient or recent organic matter (or both) produced in the atmosphere.

Chang, S.↗

Theoretical Calculation Study of Nanomaterials

In recent years, theoretical simulations using computational physics and chemistry models have been used widely to predict the physical, chemical, and structural properties of nanomaterials. To reflect such rapid progress, two Special Issues on the theoretical study of nanomaterials were published. The 36 articles collected cover broad re-search fields and applications. In this Editorial, we provide an overview of these pub-lications and summarize the main findings. Based on these research outcomes, we lay out some future research directions.

First-principles calculations↗

Biology and the Exploration of Mars

Until recent years the origin of life and its possible occurrence elsewhere in the universe have been matters for speculation only. The rapid growth of molecular biology since 1940 has, to be sure, made it possible to discuss life's origins in far more precise and explicit terms than was possible earlier; and the subject entered a new experimental phase in the 1950's with successful abiogenic synthesis of important biochemical substances in conditions simulating the presumptive environment of the primitive Earth. But the real transformation that the subject has undergone stems from the spectacular growth of space technology in the last decade. The possibility of life's origin and occurrence on planets other than ours is no longer limited to idle speculation: it has entered the realm of the testable, of science in the strict sense. Given the rockets now available, and especially those available by 1969, it has become fully realistic to consider plans for the biological exploration of Mars. The study that this report seeks to interpret was initiated in June, 1964, by the Space Science Board of the National Academy of Sciences to examine this possibility. The working group comprised 36 people representing a broad spectrum of scientific interests: evolutionary biology, genetics, microbiology, biochemistry and molecular biology, animal physiology, soil chemistry, organic chemistry, planetary astronomy, geochemistry, and theoretical physics. The participants included some with considerable prior involvement in problems of space exploration and others with none. Advice was also sought outside the group of immediate participants on the potentialities of selected analytical methods for the experimental study of extraterrestrial life and its environment. More than 30 individuals contributed in this fashion written assessments of techniques in which they were particularly well versed. Our task was to examine the scientific foundations and merits of the proposal to undertake a biological exploration of Mars. What are the potential scientific yields? How valuable, if attained, would they be? What, in fact, is the possibility of life occurring on Mars? And of our detecting it with available and foreseeable technology? What could be achieved by further astronomical work from Earth? by Martian fly-by missions? by Martian orbiters? and Martian Landers? What payloads would we recommend for planetary missions? What timing and over-all strategy would we recommend for Martian exploration were we to consider it worthwhile at all? In brief, the over-all purpose was to recommend to. the government, through the Academy's Space Science Board, whether or not a biological exploration of Mars should be included in the nation's space program over the next few decades; and, further, to outline what that program, if any, should be.

CONFERENCE↗

Early chemical history of the solar system

By using equilibrium thermodynamics, the sequence of condensation of mineral phases from a cooling nebula of solar composition has been calculated. The theoretical models suggest that the chemistry and mineralogy of Ca-Al-rich inclusions in C2 and C3 chondrites were established during condensation at temperatures above 1300 K. Fractionation of such inclusions is necessary to account for the refractory element depletions of ordinary and enstatite chondrites relative to the carbonaceous chondrites. The metal-silicate fractionation in ordinary chondrites took place in the nebula at a temperature below 1000 K and at .00001 atm total pressure. The volatile element depletion of C2 and C3 chondrites relative to C1 chondrites took place during chondrule formation: the most volatile elements are depleted in ordinary chondrites because they accreted before these elements were totally condensed.

Grossman, L.↗

Silicon material task. Part 3: Low-cost silicon solar array project

The feasibility of a process for carbon reduction of low impurity silica in a plasma heat source was investigated to produce low-cost solar-grade silicon. Theoretical aspects of the reaction chemistry were studied with the aid of a computer program using iterative free energy minimization. These calculations indicate a threshold temperature exists at 2400 K below which no silicon is formed. The computer simulation technique of molecular dynamics was used to study the quenching of product species.

Roques, R. A.↗

Physics through the 1990s: Scientific interfaces and technological applications

The volume examines the scientific interfaces and technological applications of physics. Twelve areas are dealt with: biological physics-biophysics, the brain, and theoretical biology; the physics-chemistry interface-instrumentation, surfaces, neutron and synchrotron radiation, polymers, organic electronic materials; materials science; geophysics-tectonics, the atmosphere and oceans, planets, drilling and seismic exploration, and remote sensing; computational physics-complex systems and applications in basic research; mathematics-field theory and chaos; microelectronics-integrated circuits, miniaturization, future trends; optical information technologies-fiber optics and photonics; instrumentation; physics applications to energy needs and the environment; national security-devices, weapons, and arms control; medical physics-radiology, ultrasonics, MNR, and photonics. An executive summary and many chapters contain recommendations regarding funding, education, industry participation, small-group university research and large facility programs, government agency programs, and computer database needs.

Source record↗

Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗

Isotopic Anomalies in Primitive Solar System Matter: Spin-State Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15, This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar core. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotop c enrichments measured in carbonaceous meteorites, However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores, We also show that while the nitriles, HCN and HNC, contain the greatest N-15 enrichment, this is not expected to correlate with extreme D emichment. These calculations therefore support the view that Solar System N-15 and D isotopic anomalies have an interstellar heritage, We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗

Eta Carinae & the Homunculus: Far Infrared Sub-millimeter Spectral Lines detected with the Herschel Space Observatory

The evolved massive binary star η Carinae underwent eruptive mass loss events that formed the complex bi-polar “Homunculus” nebula harboring tens of solar masses of unusually nitrogen-rich gas and dust. Despite expectations for the presence of a significant molecular component to the gas, detections have been observationally challenged by limited access to the far-infrared and the intense thermal continuum. A spectral survey of the atomic and rotational molecular transitions was carried out with theHerschel Space Observatory, revealing a rich spectrum of broad emission lines originating in the ejecta. Velocity profiles of selected PACS lines correlate well with known substructures: Hi in the central core; NH and weak [Cii] within the Homunculus; and [Nii] emissions in fast-moving structures external to the Homunculus.We have identified transitions from [Oi], Hi, and 18 separate light C- and O-bearing molecules including CO, CH, CH+, and OH, and a wide set of N-bearing molecules,NH, NH+, N2H+, NH2, NH3, HCN, HNC, CN, and N2H+. Half of these are new detections unprecedented for any early-type massive star environment. A very low ratio[12C/13C]≤4 is estimated from five molecules and their isotopologues. We demonstrate that non-LTE effects due to the strong continuum are significant. Abundance patterns are consistent with line formation in regions of carbon and oxygen depletions with nitrogen enhancements, reflecting an evolved state of the erupting star with efficient transport of CNO-processed material to the outer layers. The results offer many opportunities for further observational and theoretical investigations of the molecular chemistry under extreme physical and chemical conditions around massive stars in their final stages of evolution.

T. R. Gull↗

Forte: A suite of advanced multireference quantum chemistry methods

Software development plays a critical role in advancing quantum chemistry, enabling the exploration of new fundamental theoretical ideas and modeling systems of ever-increasing complexity. In the past decade, the availability of quantum chemistry packages that use modular designs and provide application programming interfaces (APIs) has enabled the creation of specialized software plugins, enhancing the capabilities of the original codes. Here, the availability of well-documented APIs is particularly beneficial in the context of academic scientific software development because it reduces the entry barrier for new developers and shields them from the complexities of large software projects.

74 ATOMIC AND MOLECULAR PHYSICS↗

Identifying Green Solvent Mixtures for Bioproduct Separation Using Bayesian Experimental Design

Liquid–liquid extraction (LLE) is a widely used technique for the separation and purification of liquid-phase products with applications in various industries, including pharmaceuticals, petrochemicals, and renewable chemistry. A critical step in the design of an LLE process is the selection of appropriate solvents. This study presents a new methodology for identifying solvent mixtures for bioproduct separation using Bayesian experimental design (BED). Motivated by the need for environmentally friendly and effective separation methods, we address the challenge of selecting solvent systems that balance separation efficiency, selectivity, and environmental impact while also tackling the difficulty of separating multiple bioproducts using complex solvent systems. Our approach specifically seeks to predict product partition coefficients (log10 Kp values) as thermodynamic parameters underlying solvent selection. The iterative approach integrates Bayesian optimization with experimental measurements to guide solvent selection and leverages COSMO-RS simulations to enhance high-throughput experimentation. Using the design of solvent systems for the separation of lignin-derived aromatic products via centrifugal partition chromatography (CPC) as a case study, we show that within seven iterations/cycles of the methodology, we can identify new mixtures of green solvents that align with CPC design principles. Furthermore, these results demonstrate the efficacy of the BED framework in optimizing green solvent systems for complex separations, highlighting the potential of this method to advance the field of green chemistry and contribute to the development of sustainable industrial processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon chemistry of circumstellar envelopes

The chemical composition of envelopes surrounding cool evolved stars, as determined from microwave spectroscopic observations, is reviewed. Emphasis is placed on recent observations with the new large mm-wavelength telescopes and interferometer arrays, and on new theoretical work, especially concerning ion-molecule chemistry of carbon-bearing in these envelopes. Thermal (as opposed to maser) emission lines are discussed. Much progress has been made in the past few years in the theoretical understanding of these objects. It is already clear, however, that observations with the new generation of mm-telescopes will require substantial improvements in the theoretical models to achieve a thorough understanding of the data now becoming available.

Bieging, John H.↗

Complex Organic Molecules in Star-Forming Regions of the Magellanic Clouds

The Large and Small Magellanic Clouds (LMC and SMC), gas-rich dwarf companions of the Milky Way, are the nearest laboratories for detailed studies on the formation and survival of complex organic molecules (COMs) under metal poor conditions. To date, only methanol, methyl formate, and dimethyl ether have been detected in these galaxies – all three toward two hot cores in the N113 star-forming region in the LMC, the only extragalactic sources exhibiting complex hot core chemistry. We describe a small and diverse sample of the LMC and SMC sources associated with COMs or hot core chemistry, and compare the observations to theoretical model predictions. Theoretical models accounting for the physical conditions and metallicity of hot molecular cores in the Magellanic Clouds have been able to broadly account for the existing observations, but fail to reproduce the dimethyl ether abundance by more than an order of magnitude. We discuss future prospects for research in the field of complex chemistry in the low-metallicity environment. The detection of COMs in the Magellanic Clouds has important implications for astrobiology. The metallicity of the Magellanic Clouds is similar to galaxies in the earlier epochs of the Universe, thus the presence of COMs in the LMC and SMC indicates that a similar prebiotic chemistry leading to the emergence of life, as it happened on Earth, is possible in low-metallicity systems in the earlier Universe.

Magellanic Clouds, star formation, astrochemistry,↗

Complex Organic Molecules in the Star-Forming Regions of the Magellanic Clouds

The Large and Small Magellanic Clouds (LMC and SMC), gas-rich dwarf companions of the Milky Way, are the nearest laboratories for detailed studies on the formation and survival of complex organic molecules (COMs) under metal-poor conditions. To date, only methanol, methyl formate, and dimethyl ether have been detected in these galaxiesall three toward two hot cores in the N113 star-forming region in the LMC, the only extragalactic sources exhibiting complex hot-core chemistry. We describe a small and diverse sample of the LMC and SMC sources associated with COMs or hot-core chemistry, and compare the observations to theoretical model predictions. Theoretical models accounting for the physical conditions and metallicity of hot molecular cores in the Magellanic Clouds have been able to broadly account for the existing observations, but they fail to reproduce the dimethyl ether abundance by more than an order of magnitude. We discuss future prospects for research in the eld of complex chemistry in the low- metallicity environment. The detection of COMs in the Magellanic Clouds has important implications for astrobiology. The metallicity of the Magellanic Clouds is similar to that of galaxies in the earlier epochs of the universe; thus, the presence of COMs in the LMC and SMC indicates that a similar prebiotic chemistry leading to the emergence of life, as it happened on Earth, is possible in low-metallicity systems in the earlier universe.

Sewilo, Marta M.↗

Physics and Chemistry of Te and HgTe-based Ternary Melts

Historically, the theoretical treatment of the liquid phases has always been more difficult and complicated than that for solid and gas phases. A liquid has no lattice structure as crystalline solids and the atoms/molecules in the liquid can migrate through it relatively rapidly. On the other hand, it is also interacting with many other atoms/molecules so that the simplifications of the kinetic theory of gases cannot be employed. For more complicated liquids, such as the liquids of high ionicity and those containing hydrogen bonds and electric dipoles, the understanding is far from complete. At the same time, accurate information on the physics and chemistry of semiconductor melts is needed for the quantitative descriptions of the process of crystal growth from melt. The pre-crystallization phenomena in the liquid phase are critical because the properties of the grown crystals depend on the state and structure of the melt as well as the thermal history of the melt during solidification process. However, the data on the liquid phase, such as thermophysical properties of semiconductor melts are scarce, especially for the HgTe-based II-VI ternary compound semiconductors because of their high vapor pressure and extreme toxicity. Analysis of the thermophysical properties of the melt can provide information about structural transitions of the melt during the solidification process. From a broader point of view, the structure of liquids is much more complicated than the crystalline solids, especially the relaxation behavior through different thermal histories. The theory of hetero-phase fluctuations of liquids is applicable to any many-body systems including condensed-matter physics, field theory, physics of nuclear-matter, cosmology, biology and even sociology. This book summarizes the physics and chemistry from the experimental measurements and theoretical analyses of phase diagram, thermodynamic properties, density, thermal conductivity, viscosity, and electrical conductivity on the binary, pseudo-binary and ternary melts of the most advanced IR-detector material systems of HgCdTe and HgZnTe as well as the analyses of these results. The main objectives of this study are: (1) to provide the phase diagrams and thermodynamic properties of Hg-Cd-Te and Hg-Zn-Te systems through quantitatively fitting the experimental data by assuming an associated solution model for the liquid phase, (2) to experimentally measure the thermophysical properties of the Hg-Cd-Te and Hg-Zn-Te melts, including density, viscosity, electrical conductivity and thermal conductivity as functions of temperature and composition and (3) to enhance the fundamental knowledge of hetero-phase fluctuations and relaxation phenomena in the melts and extend our understanding of the solidification process in order to interpret the experimental results of crystal growth so as to improve the melt growth processes of the compound semiconductor. The physics and chemistry of Te and HgTe-based ternary melts were explored through the studies of the structural transformation during melting, the supercooling during solidification, the relaxation phenomena after rapid cooling of the melts and the metal-semiconductor transition in the melts through the analyses of electrical conductivity and Lorenz number. An in-depth study on the thermophysical properties and their time-dependent structural dynamic processes taking place in the vicinity of the solid-liquid phase transition of the narrow homogeneity range HgTe-based ternary semiconductors as well as the analysis of the homogenization process in the melt will also be presented.

Thermophysical properties↗

Minor constituents in the stratosphere and mesosphere

A review of the research in minor constituents in the stratosphere and mesosphere, carried out between 1975 and 1978, is presented. Much of the theoretical research was done with the aid of one-dimensional models. Different aspects of these models are discussed. Measurements of the chlorofluoromethanes, hydrochloric acid, nitric oxide, nitrous oxide, and hydrogen oxide were conducted. It is noted that the hydrogen oxides are now assuming a larger role in stratospheric photochemistry than have been postulated before. The effect of water vapor and the hydrogen oxides on the overall chemistry of the stratosphere was investigated theoretically, along with the possible relationship between solar activity and atmospheric ozone. The mesosphere study included ozone, water vapor, nitric oxide, and odd nitrogen investigations.

Hudson, R. D.↗