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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1996

IRAS Colors of the Pleiades

We present large scale images of the infrared emission of the region around the Pleiades using the ISSA data product from the IRAS mission. Residual Zodiacal background and a discontinuity in the image due to the scanning strategy of the satellite necessitated special background subtraction methods. The 60/100 color image clearly shows the heating of the ambient interstellar medium by the cluster. The 12/100 and 25/100 images peak on the cluster as expected for exposure of small dust grains to an enhanced UV radiation field; however, the 25/100 color declines to below the average interstellar value at the periphery of the cluster. Potential causes of the color deficit are discussed. A new method of identifying dense molecular material through infrared emission properties is presented. The difference between the 100 micron flux density and the 60 micron flux density scaled by the average interstellar 60/100 color ratio (Delta I(sub 100) is a sensitive diagnostic of material with embedded heating sources (Delta I(sub 100) less than 0) and cold, dense cores (Delta I(sub 100) greater than 0). The dense cores of the Taurus cloud complex as well as Lynds 1457 are clearly identified by this method, while the IR bright but diffuse Pleiades molecular cloud is virtually indistinguishable from the nearby infrared cirrus.

Carey, Sean J.↗
NASA NTRS1981

The extinction toward the galactic center from observations of interstellar lines

H2CO absorption observations against Sgr A are used to select the molecular material lying in front of the galactic center, and an analysis similar to that of Blitz and Shu (1980) is carried out. The ratio of visual extinction to equivalent width of the 6 cm line of H2CO is found to be similar for several nearby interstellar clouds. By considering only the molecular components in front of the infrared cluster, the estimate for the extinction is decreased to 15-46 mag. These results are consistent with those from infrared observations toward the galactic center. Extinction estimates based on other interstellar species are also considered. Atomic gas is seen as contributing less than 10 mag of extinction.

Federman, S. R.↗
NASA NTRS2016

A Search for O2 in CO-Depleted Molecular Cloud Cores With Herschel

The general lack of molecular oxygen in molecular clouds is an outstanding problem in astrochemistry. Extensive searches with the Submillimeter Astronomical Satellite, Odin, and Herschel have only produced two detections; upper limits to the O2 abundance in the remaining sources observed are about 1000 times lower than predicted by chemical models. Previous atomic oxygen observations and inferences from observations of other molecules indicated that high abundances of O atoms might be present in dense cores exhibiting large amounts of CO depletion. Theoretical arguments concerning the oxygen gas-grain interaction in cold dense cores suggested that, if O atoms could survive in the gas after most of the rest of the heavy molecular material has frozen out onto dust, then O2 could be formed efficiently in the gas. Using Herschel HIFI, we searched a small sample of four depletion cores-L1544, L694-2, L429, and Oph D-for emission in the low excitation O2 N(sub J)=3(sub 3)-1(sub 2) line at 487.249 GHz. Molecular oxygen was not detected and we derive upper limits to its abundance in the range of N(O2)/N (H2) approx. = (0.6-1.6) x10(exp -7). We discuss the absence of O2 in the light of recent laboratory and observational studies.

ISM: abundances↗
NASA NTRS2011

Process for derivatizing carbon nanotubes with diazonium species and compositions thereof

Methods for the chemical modification of carbon nanotubes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications, and sensor devices. The methods of derivatization include electrochemical induced reactions, thermally induced reactions, and photochemically induced reactions. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes.

Tour, James M.↗
DOE OSTI2020

Machine learning for collective variable discovery and enhanced sampling in biomolecular simulation

Classical molecular dynamics simulates the time evolution of molecular systems through the phase space spanned by the positions and velocities of the constituent atoms. Molecular-level thermodynamic, kinetic, and structural data extracted from the resulting trajectories provide valuable information for the understanding, engineering, and design of biological and molecular materials. The cost of simulating many-body atomic systems makes simulations of large molecules prohibitively expensive, and the high-dimensionality of the resulting trajectories presents a challenge for analysis. Driven by advances in algorithms, hardware, and data availability, there has been a flare of interest in recent years in the applications of machine learning – especially deep learning – to molecular simulation. Furthermore, these techniques have demonstrated great power and flexibility in both extracting mechanistic understanding of the important nonlinear collective variables governing the dynamics of a molecular system, and in furnishing good low-dimensional system representations with which to perform enhanced sampling or develop long-timescale dynamical models. It is the purpose of this article to introduce the key machine learning approaches, describe how they are married with statistical mechanical theory into domain-specific tools, and detail applications of these approaches in understanding and accelerating biomolecular simulation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Probing transport energies and defect states in organic semiconductors using energy resolved electrochemical impedance spectroscopy

Abstract Determining the relative energies of transport states in organic semiconductors is critical to understanding the properties of electronic devices and in designing device stacks. Futhermore, defect states are also highly important and can greatly impact material properties and device performance. Recently, energy‐resolved electrochemical impedance spectroscopy (ER‐EIS) is developed to probe both the ionization energy (IE) and electron affinity (EA) as well as sub‐bandgap defect states in organic semiconductors. Herein, ER‐EIS is compared to cyclic voltammetry (CV) and photoemission spectroscopies for extracting IE and EA values, and to photothermal deflection spectroscopy (PDS) for probing defect states in both polymer and molecular organic semiconductors. The results show that ER‐EIS determined IE and EA are in better agreement with photoemission spectroscopy measurements as compared to CV for both polymer and molecular materials. Furthermore, the defect states detected by ER‐EIS agree with sub‐bandgap features detected by PDS. Surprisingly, ER‐EIS measurements of regiorandom and regioregular poly(3‐hexylthiophene) (P3HT) show clear defect bands that occur at significantly different energies. In regioregular P3HT the defect band is near the edge of the occupied states while it is near the edge of the unoccupied states in regiorandom P3HT.

14 SOLAR ENERGY↗
DOE OSTI2026

Understanding and Controlling Photoexcited Molecules in Complex Environments (Final Technical Report)

Predicting the outcome of a photochemical reaction is complicated by factors outside the scope of tradition theoretical chemistry. On such small scales, fluctuations of the environment render outcomes stochastic, nonadiabatic dynamics blur the separation between nuclear and electronic motion, and ultrafast relaxation renders typical assumptions of equilibrium inappropriate. This project aimed to elucidate and control nonadiabatic molecular dynamics in condensed phases. We developed accurate, efficient simulation tools to study irreversible molecular processes computational across a range of scales. We applied these methodological advances to study electron transfer under exotic conditions where spin and topology opened new pathways for reactivity. We also brought these ideas to bare on light harvesting systems, where energy and charge transport are coupled, and where long lifetimes can be deleterious to function. These advances helped to establish general principles for chemical efficiency and guide the design of nanoscale energy materials, molecular machines, and related technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Star formation in the Galactic Center GMC cores: Sagittarius B2 and the dust ridge

The total far-infrared luminosity and the ionizing flux inferred from radio continuum observations of the Galactic center region imply a rate of star formation per unit mass of molecular material comparable to that in the Galactic disk. However, H2O and OH masers commonly found in sites of high-mass star formation are relatively rare in the nuclear disk. Far-infrared studies suggest that the formation rate of stars with masses greater than approximately 20 Solar Mass is reduced in the central region compared to the Galactic disk. Star formation might be suppressed currently in the central region as a result of the different geometry and strength of the magnetic fields there, which arguably might tend to inhibit cloud collapse. High gas pressures implied by observations of the diffuse X-ray emission suggest that giant molecular clouds (GMCs) in the nuclear disk may be held together by external pressure rather than self-gravity. The gravitational collapse leading to the formation of high density cores may thus be suppressed in all but the most massive clouds.

Lis, D. C.↗
NASA NTRS2007

Process for derivatizing carbon nanotubes with diazonium species

The invention incorporates new processes for the chemical modification of carbon nanotubes. Such processes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications and sensor devices. The methods of derivatization include electrochemical induced reactions thermally induced reactions (via in-situ generation of diazonium compounds or pre-formed diazonium compounds), and photochemically induced reactions. The derivatization causes significant changes in the spectroscopic properties of the nanotubes. The estimated degree of functionality is ca. 1 out of every 20 to 30 carbons in a nanotube bearing a functionality moiety. Such electrochemical reduction processes can be adapted to apply site-selective chemical functionalization of nanotubes. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes ##STR00001##.

Tour, James M.↗
NASA NTRS1986

High resolution observations of the L1551 bipolar outflow

The nearby dark cloud Lynds 1551 contains one of the closest examples of a well-collimated bipolar molecular outflow. This source has the largest angular size of any known outflow and was the first bipolar outflow to be detected. The outflow originates from a low-luminosity young stellar object, IRS-5. Optical and radio continuum observations show the presence of a highly collimated, ionized stellar wind orginating from close to IRS-5 and aligned with the molecular outflow. However, we have little information on the actual mechanism that generates the stellar wind and collimates it into opposed jets. The Very Large Array (VLA) observations indicate that the winds originate within 10(15) cm of IRS-5, unfortunately at a size scale difficult to resolve. For these reasons, observations of the structure and dynamics of the hypersonic molecular gas may provide valuable information on the origin and evolution of these outflows. In addition, the study of the impact of the outflowing gas on the surrounding molecular material is essential to understand the consequence these outflows have on the evolution and star formation history of the entire cloud. Moriarty-Schieven et al. (1986) obtained a oversampled map of the CO emission of a portion of both the blueshifted and redshifted outflows in LI551 using Five College Radio Astronomy Observatory 14 m telescope. The oversampled maps have been reconstructed to an effective angular resolution of 20 arcsec using a maximum entropy algorithm. A continuation of the study of Moriarty-Schieven et al. is presented. The entire L1551 outflow has now been mapped at 12 arcsec sampling requiring roughly 4000 spectra. This data has been constructed to 20 arcsec resolution to provide the first high resolution picture of the entire L1551 outflow. This new data has shown that the blueshifted lobe is more extended than previously thought and has expanded downstream sufficiently to break out of the dense molecular cloud, but the redshifted outflow is still confined within the molecular cloud. Details of the structure and kinematics of the high velocity gas are used to test the various models of the origin and evolution of outflows.

Snell, R.↗
DOE OSTI2025

Lattice Structure and Dynamics of Sparse Molecular Crystals: OsO 4 and RuO 4

OsO 4 and RuO 4 are molecular oxides with unique tetrameric structures and rare +8 oxidation states. Accurately modeling their properties remains challenging for density functional theory (DFT) due to weak intertetramer interactions, which standard functionals fail to capture. Here, in this work, we show that the van der Waals (vdW)-corrected density functional (vdW-DF-optB86b) provides structural parameters that are much closer to experimental values than the standard generalized gradient approximation, with volume predictions that fall within the experimentally observed range. Phonon band structure analysis shows that the inclusion of vdW interactions stabilizes soft phonon modes, highlighting the importance of dispersion corrections for accurate predictions of lattice dynamics. Experimental measurements of the phonon density of states for OsO 4 , obtained via inelastic neutron scattering, demonstrate good agreement with our vdW-DF-optB86b calculations. These results validate OsO 4 and RuO 4 as valuable benchmarks for structural and vibrational calculations via vdW-corrected DFT methods and offer insights for studying the broader class of sparse molecular materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Giant and Reversible Barocaloric Effect in Trinuclear Spin–Crossover Complex Fe 3 (bntrz) 6 (tcnset) 6

A giant barocaloric effect (BCE) in a molecular material Fe 3 (bntrz) 6 (tcnset) 6 (FBT) is reported, where bntrz = 4-(benzyl)-1,2,4-triazole and tcnset = 1,1,3,3-tetracyano-2-thioethylepropenide. The crystal structure of FBT contains a trinuclear transition metal complex that undergoes an abrupt spin-state switching between the state in which all three FeII centers are in the high-spin (S = 2) electronic configuration and the state in which all of them are in the low-spin (S = 0) configuration. Despite the strongly cooperative nature of the spin transition, it proceeds with a negligible hysteresis and a large volumetric change, suggesting that FBT should be a good candidate for producing a large BCE. Powder X-ray diffraction and calorimetry reveal that the material is highly susceptible to applied pressure, as the transition temperature spans the range from 318 at ambient pressure to 383 K at 2.6 kbar. Despite the large shift in the spin-transition temperature, its nonhysteretic character is maintained under applied pressure. Such behavior leads to a remarkably large and reversible BCE, characterized by an isothermal entropy change of 120 J kg –1 K –1 and an adiabatic temperature change of 35 K, which are among the highest reversible values reported for any caloric material thus far.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Giant Magnetoelectric Coupling and Magnetic-Field-Induced Permanent Switching in a Spin Crossover Mn(III) Complex

We investigate giant magnetoelectric coupling at a Mn 3+ spin crossover in [Mn III L]BPh 4 (L = (3,5-diBr-sal) 2 323) with a field-induced permanent switching of the structural, electric, and magnetic properties. An applied magnetic field induces a first-order phase transition from a high spin/low spin (HS-LS) ordered phase to a HS-only phase at 87.5 K that remains after the field is removed. We observe this unusual effect for DC magnetic fields as low as 8.7 T. The spin-state switching driven by the magnetic field in the bistable molecular material is accompanied by a change in electric polarization amplitude and direction due to a symmetry-breaking phase transition between polar space groups. The magnetoelectric coupling occurs due to a γη 2 coupling between the order parameter γ related to the spin-state bistability and the symmetry-breaking order parameter η responsible for the change of symmetry between polar structural phases. We also observe conductivity occurring during the spin crossover and evaluate the possibility that it results from conducting phase boundaries. We perform ab initio calculations to understand the origin of the electric polarization change as well as the conductivity during the spin crossover. Thus, in this work, we demonstrate a giant magnetoelectric effect with a field-induced electric polarization change that is 1/10 of the record for any material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Anisotropic Hot Spot Formation at a Grain Boundary in Shock-Compressed TATB High Explosive Crystal

Secondary high explosives (HEs) exhibit rich microstructure that promotes the formation of hot spots responsible for detonation initiation, but the role of microstructural interfaces remains poorly quantified. To this end, we develop extensions for the generalized crystal-cutting method (GCCM) to prepare molecular dynamics (MD) simulation cells containing grain boundaries (GBs) and other crystal–crystal interfaces with prescribed tilt and twist orientations. Using the GCCM, we perform MD simulations of shock interactions with a GB between the (001) and (100) crystal facets in the secondary HE TATB (1,3,5-triamino-2,4,6-trinitrobenzene). Our MD simulations reveal a strong directional dependence to the formation of a hot spot at the GB interface. In particular, transmission of the shock from the (001) grain to the (100) grain yields a hot spot in the (100) grain at the GB interface, whereas no hot spot is produced when an equivalent shock transits the GB in the opposite direction. We trace the origin of this GB anisotropy to three dominant factors: (1) the intrinsic differences in shock-deformation mechanisms and wave structures for the bulk (100) and (001) grains, which leads to distinct geometries and mechanical impedances upon shock arrival to the GB depending on which grains are donor or acceptor for the transmitted shock; (2) the different time intervals separating the initial shock rise and the formation of steady wave structures in the respective donor–acceptor configurations; and (3) the differences in time scales required to re-establish local thermal equilibrium. Interfacial hot spots form when these factors combine to impede development of a steady two-wave structure and instead induce a localized, pseudosingly shocked region that undergoes a higher rate of work production (resulting in a higher temperature) compared to when the steady two-wave structure develops further from the interface. The extensions to the GCCM approach presented here are anticipated to facilitate a wide range of MD studies that focus on understanding the role of crystal–crystal interfaces in molecular materials.

organic↗
DOE OSTI2025

Automated Redox Titrations via Interdigitated Electrode Arrays: Application to the Mediated Electron Transfer Interrogation of Charge and Rate on Electrodeposited Polymers

Mediated electron transfer (MET) plays a crucial role in energy storage and conversion technologies such as redox targeting flow batteries (RTFBs), yet its experimental investigation often requires labor-intensive and low-throughput setups. To address this, we developed a microfabricated interdigitated electrode array (IDA) platform that enables automated, high-throughput electrochemical redox titration measurement to be performed to study the MET process. Our redox titration method enables simultaneous measurement of the charge capacity and rate of MET processes on a material or surface. Automated redox titration (ART) facilitates systematic investigation of the MET process across a broad parameter space, exemplified through the study of polypyrrole (PPy) and a pyrene-4,5,9,10-tetrone azo group-based polymer (PTAP), both redox-active polymers relevant to various energy storage applications. Using PPy as a model material, 500 redox titration measurements were conducted within 50 h, varying the electrode gap widths, polymer charging potentials, voltammetric scan rates, and electrolyte concentrations. Finite-element simulations confirmed the electrochemical responses and elucidated the kinetics of the MET reactions. Our automated methodology was further tested with PTAP, revealing a surprising charging potential dependence on the rate of MET. The automation, flexibility, and scalability of our redox titration platform pave the way not only for advanced studies of MET processes relevant to RTFBs, but also with implications in the understanding of next-generation energy storage materials, molecular electrocatalysis, and biosensing.

electrochemical analysis↗
DOE OSTI2025

Vibrational Dynamics and Phase Transitions of Hydrazine to 50 GPa

The high pressure behavior of hydrazine, N 2 H 4 , has been investigated to 50 GPa at room temperature using infrared and Raman spectroscopy to explore pressure induced phase transitions and changes in hydrogen bonding. Three solid–solid phase transitions were detected at 11, 21, and 32 GPa on room temperature compression through dramatic changes in the lattice vibration and N–H stretching regions with increasing pressure in both measurement techniques. The transition to phase IV, which appears at 32 GPa, exhibits increased hydrogen bonding with significant hysteresis, persisting to 9 GPa on decompression. This work presents a detailed analysis of the pressure dependence of mode shifts and calculations of mode Grüneisen parameters as well as a determination of an approximate thermodynamic Grüneisen parameter. We compare these results to the behavior of other small molecular materials such as ammonia and water and explore the evolution of hydrogen bonding in hydrazine toward the symmetrically hydrogen bonded state, which has previously been suggested by theoretical computations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

π-Extended Porphyrin–Phthalocyanine Heterojunction Devices Exhibiting High Ammonia Sensitivity with a Remarkable Light Effect

π-Extended porphyrins represent an attractive class of organic compounds because of their unique photophysical, optoelectronic, and physicochemical properties. Herein, cross-conjugated (Ace-PQ-Ni) and linear-conjugated (AM6) porphyrins are used to build double-layer heterojunction devices by combining them with a lutetium bisphthalocyanine complex (LuPc 2 ). The heterojunction effect at the porphyrin–phthalocyanine interface plays a key role in the charge transport properties. Both devices exhibit exceptionally high ammonia sensitivity at room temperature and under ambient relative humidity, with limit of detection values of 156 and 115 ppb for Ace-PQ-Ni/LuPc 2 and AM6/LuPc 2 sensors, respectively. Interestingly, the Ace-PQ-Ni/LuPc 2 and AM6/LuPc 2 sensors display opposite effects upon light illumination. While the former sensors show largely decreased ammonia sensitivity under light illumination, the current variation of the latter under ammonia is remarkably enhanced with a multiplication factor of 13 and a limit of detection (LOD) of 83 ppb. Here, the striking difference in their sensing properties upon light illumination is attributed to their different π-conjugation pathways (cross-conjugation versus linear conjugation).

conductometric transducer↗
DOE OSTI2025

Air-Enabled Electricity-Driven Depolymerization of Polyesters

This work describes the use of electrochemically generated superoxide (with air as the source of O 2 ) at carbon electrodes as a reagent for the depolymerization of polyesters. Here, we report the electricity-driven selective conversion of these common ester-based wastes into their foundational carboxylate and alkoxide building blocks. The results pave the way for an electrochemical approach to the recovery of molecular materials from ester wastes that uses air and electricity as key reagents for material recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗