Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “molecular materials”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Thermal Hydroquinone Oxidation on Co/N-doped Carbon Proceeds by a Band-Mediated Electrochemical Mechanism

Molecules catalyze aerobic oxidation reactions via redox cycling at the metal center to effect sequential activation of O 2 and the substrate. Metal surfaces can catalyze the same transformations by coupling independent half-reactions for oxygen reduction and substrate oxidation mediated via the exchange of band-electrons. Metal/nitrogen-doped carbons (MNCs) are promising catalysts for aerobic oxidation that consist of molecule-like active sites embedded in a conductive carbon host. Owing to their combining molecular and metallic features, it remains unclear whether they proceed via the sequential redox cycling pathways of molecules or the band-mediated pathways of metals. Herein, we simultaneously track the potential of the catalyst and the rate of the turnover of aerobic hydroquinone oxidation on a cobalt-based MNC catalyst contacted to a catalytically inactive carbon electrode. By comparing operando measurements of rate and potential with the current-voltage behavior of each constituent half-reaction under identical conditions, we show that these molecular materials can display the band-mediated reaction mechanisms of extended metallic solids. Further, we show that the action of these band-mediated mechanisms explains fractional reaction orders in both oxygen and hydroquinone, the time evolution of catalyst potential and rate, and the dependence of rate on overall reaction free energy. Selective poisoning experiments suggest that oxygen reduction proceeds at cobalt sites, whereas quinone oxidation proceeds at native oxidic defects on the carbon. These findings highlight that molecule-like active sites can take advantage of band-mediated mechanisms when coupled to conductive hosts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Investigating the electronic structure of high explosives with X-ray Raman spectroscopy

Abstract We investigate the sensitivity and potential of a synergistic experiment-theory X-ray Raman spectroscopy (XRS) methodology on revealing and following the static and dynamic electronic structure of high explosive molecular materials. We show that advanced ab-initio theoretical calculations accounting for the core-hole effect based on the Bethe-Salpeter Equation (BSE) approximation are critical for accurately predicting the shape and the energy position of the spectral features of C and N core-level spectra. Moreover, the incident X-ray dose typical XRS experiments require can induce, in certain unstable structures, a prominent radiation damage at room temperature. Upon developing a compatible cryostat module for enabling cryogenic temperatures ( $$\approx$$ ≈ 10 K) we suppress the radiation damage and enable the acquisition of reliable experimental spectra in excellent agreement with the theory. Overall, we demonstrate the high sensitivity of the recently available state-of-the-art X-ray Raman spectroscopy capabilities in characterizing the electronic structure of high explosives. At the same time, the high accuracy of the theoretical approach may enable reliable identification of intermediate structures upon rapid chemical decomposition during detonation. Considering the increasing availability of X-ray free-electron lasers, such a combined experiment-theory approach paves the way for time-resolved dynamic studies of high explosives under detonation conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Simulation of ultrafast transient absorption spectra of a perylene-based light harvesting antenna

Atomistic simulations of photo-induced responses in artificial light-harvesting molecular systems help to reveal the mechanisms of ultrafast intramolecular energy transfer between individual chromophores. These light-induced processes mimic the primary events occurring in natural photosynthesis. Modeling studies contribute to the design of more efficient molecular architectures enabling performance optimization for applications in light harvesting, energy conversion, and optoelectronics. Within this context, the direct comparison between simulated and experimental transient absorption pump–probe (TA-PP) spectra are especially valuable for validating theoretical approaches and deepening mechanistic understanding. Herein, we investigate the photoinduced dynamics of an antenna system composed of two naphthalene monoimides donor units covalently linked to a perylene derived acceptor. Following photoexcitation, the exciton rapidly self-traps on one of the donor units. Thereafter, efficient ultrafast energy transfer to the acceptor unit takes place via two possible pathways: either through transient exciton localization on the second donor unit or by direct transfer to the acceptor. The simulated TA-PP spectra clearly capture these distinct energy transfer pathways and enable a detailed comparison of their relative efficiencies. This highlights the system's potential for tunable exciton dynamics towards advancing light-harvesting and optoelectronic molecular materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Accurate energies for ππ* excited states via exchange scaling: the XS-CASSCF method

The state-averaged complete-active space self-consistent field method (SA-CASSCF) is a widely employed electronic structure method used for studying photochemistry and dynamics owing to its ability to provide a reliable description even of complicated cases while still retaining computational efficiency. However, SA-CASSCF suffers from one Achilles heel, related to the description of ionic ππ* excited states, whose energy is often overestimated by 1–2 eV. In light of this challenge, we present the XS-CASSCF method, a new approach based on the idea of exchange scaling (XS) that screens the involved energy terms to improve the excitation energies of singlet ionic ππ* states. First, we illustrate the power of the XS-CASSCF method using hexatriene and para-quinodimethane as examples, showing that it corrects the targeted ionic states while leaving the other states largely unaffected, giving root-mean-square errors (RMSE) below 0.2 eV for the four lowest states in both cases. Subsequently, XS-CASSCF vertical excitation energies are tested against theoretical best estimates for a set of 11 molecules and 56 excited states. XS-CASSCF performs exceptionally well for the ππ* states of hydrocarbons, reducing the RMSE over 21 excitation energies from 0.96 to 0.27 eV. In the challenging subset of molecules with heteroatoms and a larger number of ππ* and nπ* states, we find that improvements can also be obtained, albeit not as pronounced. We conclude with an outlook into more realistic molecular materials focusing on their singlet–triplet (S 1 /T 1 ) gaps, finding that significant improvements can be obtained along the whole range of S 1 /T 1 gaps studied, going from 0.1 eV to more than 1.5 eV. Owing to notable improvements across significant classes of molecules combined with its conceptual simplicity, we believe that XS-CASSCF is a promising addition to the electronic structure toolbox, serving both as a standalone electronic structure method and as a starting point for further correlated treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Vibrational spectroscopy of shock compressed condensed phase nitrous oxide: Frequency shifts in the ν 1 mode

Over many years, we have published vibrational spectra of molecular materials at extreme pressure and temperature obtained using shock compression and coherent Raman spectroscopy methods. For diatomic molecules, we were able to extract vibrational temperatures from the intensities of spectrally resolved vibrational hot bands. Larger molecules in the condensed phase suffer band broadening effects that obscure the vibrational hot bands as the anharmonicities are typically smaller than the widths of the bands. This inability to resolve the hot bands inhibits the extraction of vibrational temperature and the measurement of the vibrational frequency of the fundamental. Here, we use a hot band model based on gas-phase anharmonic coupling coefficients to fit coherent anti-Stokes Raman spectra of the ν 1 vibrational mode of shock compressed condensed phase N 2 O with shock pressures and temperatures estimated from literature equations of state and compare to fits from a model using a single Gaussian peak. We report the resulting vibrational frequency shifts with shock pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2020

chimes_calculator

The Chebyshev Interaction Model for Efficient Simulation (ChIMES) is a machine-learned interatomic potential targeting chemistry in condensed phase systems. ChIMES models are able to approach quantum-accuracy through a systematically improvable explicitly many-bodied basis comprised of linear combinations of Chebyshev polynomials. Though originally developed as to enable description of organic molecular materials, ChIMES has successfully been applied to systems spanning ambient water to molten carbon, and leveraged as correction for density functional based tight binding simulations. The ChIMES calculator comprises a flexible toolset for evaluating ChIMES interactions (e.g. in simulations, single point calculations, etc). Users have the option of directly imbedding the ChIMES calculator within their codes, or evaluating interactions through the beginner-friendly serial interface, each of which have Python, C++, C, and Fortran API's.

Goldman, Nir↗
DOE OSTI2024

Reversible Surface Energy Storage in Molecular-Scale Porous Materials

Forcible wetting of hydrophobic pores represents a viable method for energy storage in the form of interfacial energy. The energy used to fill the pores can be recovered as pressure–volume work upon decompression. For efficient recovery, the expulsion pressure should not be significantly lower than the pressure required for infiltration. Hysteresis of the wetting/drying cycle associated with the kinetic barrier to liquid expulsion results in energy dissipation and reduced storage efficiency. In the present work, we use open ensemble (Grand Canonical) Monte Carlo simulations to study the improvement of energy recovery with decreasing diameters of planar pores. Near-complete reversibility is achieved at pore widths barely accommodating a monolayer of the liquid, thus minimizing the area of the liquid/gas interface during the cavitation process. At the same time, these conditions lead to a steep increase in the infiltration pressure required to overcome steric wall/water repulsion in a tight confinement and a considerable reduction in the translational entropy of confined molecules. In principle, similar effects can be expected when increasing the size of the liquid particles without altering the absorbent porosity. While the latter approach is easier to follow in laboratory work, we discuss the advantages of reducing the pore diameter, which reduces the cycling hysteresis while simultaneously improving the stored-energy density in the material.

36 MATERIALS SCIENCE↗
NASA NTRS1987

IRAS and ground-based observations of star formation regions in the Magellanic clouds

The Infrared Astronomy Satellite (IRAS) detected several hundred individual regions of star formation in the Large and Small Magellanic Clouds. Nearly two dozen of the brightest such sources were searched for from the ground at 10 microns; most of these were located and measured at wavelengths from 0.6 to 20 microns. Three principle results emerge from this study: First, the IRAS data show that star formation is considerably less active in the SMC than in the LMC, relative either to mass, luminosity, or H I content. The reduced activity in the SMC is consistent with the smaller amount of molecular material inferred from CO observations. Second, the sizes of the objects range from less than a few arcsecs (objects which look like extremely compact HII regions, with little or no extended radio, optical, or infrared emission) to some tens of arcsecs across (giant HII regions, of which the largest and brightest is 30 Doradus). Third, there are no obvious differences in the characteristics of the central portions of the LMC and SMC sources; all look like Galactic H II regions of similar luminosity.

Elias, Jonathan H.↗
NASA NTRS1987

Observations of 1.3 millimeter continuum emission from the centers of galaxies

A search for 1.3 mm continuum emission from the centers of eight galaxies has been conducted, and three sources of emission, all apparently arising from cold dust, have been detected. The gas mass associated with this dust is calculated. A rough correlation found between the J = 1-0 CO emission and the millimeter continuum flux, as well as a fair agreement between the masses determined from the two types of observation, support the view that the cool dust is mixed with the molecular material in the program objects. Atomic hydrogen masses estimated for the same cources from 21 cm line observations show that there is little H I in the objects. Most of the objects form stars at about the same efficiency as does the Galaxy.

Thronson, Harley A., Jr.↗
NASA NTRS1988

Submillimeter and far-infrared line observations of M17 SW - A clumpy molecular cloud penetrated by ultraviolet radiation

Millimeter, submillimeter, and far-IR spectroscopic observations of the M17 SW star formation region are reported. Strong forbidden C II 158 micron and CO J = 7 - 6 line emission arises in an H II region/molecular cloud interface of several pc thickness. Weaker forbidden C II emission appears to be extended over 15 pc throughout the molecular cloud. CO J = 14 - 13 and forbidden O I 145 micron spectra indicate high temperatures and densities for both molecular and atomic gas in the interface. The results require the molecular cloud near the interface to be clumpy or filamentary. The extended forbidden C II emission throughout the molecular cloud has a level around 20 times higher than expected from a single molecular cloud interface exposed to an ultraviolet radiation field typical of the solar neighborhood. The high gas temperature of molecular material in the UV-illuminated interface region suggests that CO self-shielding and heating of CO by photoelectrons are important.

Stutzki, J.↗
NASA NTRS1989

A study of the stellar population in the Lynds 1641 dark cloud - A possible dense cluster associated with IRAS 05338-0624

Sensitive images obtained at 1.6 and 2.2 microns reveal a possible dense cluster of stars associated with IRAS 05338-0624 and located within an optically thick molecular core; the visual extinction suffered by cluster members ranges from 7 to 40 mag. A circular region of diameter 70 arcsec (0.16 pc at a distance of 480 pc) contains 20 stellar objects or semistellar knots. Assuming that the depth of the region is comparable to its projected size leads to an estimated stellar density of 6800/cu pc. The ratio of stellar to molecular material contained within the core must lie between 4 percent and 43 percent. It is likely that this cluster will emerge from its parent core as a bound group.

Strom, Karen M.↗
NASA NTRS1990

The hot and cold interstellar matter of early type galaxies and their radio emission

Over the last few years, the knowledge of the interstellar matter (ISM) of early type galaxies has increased dramatically. Many early type galaxies are now known to have ISM in three different phases: cold (neutral hydrogen (HI), dust and molecular material), warm (ionized) and hot (S-ray emitting) gas. Early type galaxies have smaller masses of cold ISM (10 to the 7th power - 10 to the 8th power solar mass; Jura et al. 1987) than later type spiral galaxies, while they have far more hot gas (10 to the 9th power - 10 to the tenth power solar mass; Forman et al. 1985, Canizares et al. 1987). In order to understand the relationship between the different phases of the ISM and the role of the ISM in fueling radio continuum sources and star formation, researchers compared observational data from a wide range of wavelengths.

Kim, Dong-Woo↗
NASA NTRS1991

Young stellar objects detected by IRAS

Fluxes of 453 IRAS point sources selected for proximity to dense gas have been accurately determined by co-adding IRAS data. From this set, 258 sources are detected in all four bands: 12, 25, 60, and 100 microns. As distance from dense molecular material increases, these sources exhibit systematic trends in color and a markedly decreasing luminosity. These trends are broadly consistent with expected evolutionary changes in these stars, with younger objects found closer to dense gas. These data suggest a subtle variation on the criterion for identifying the youngest objects detectable by IRAS, in addition to that of steeply rising spectra: a color temperature which is uniform across all four IRAS bands in the range 40-50 K. These characteristics are used as a criterion to select point sources as candidate very young pre-main-sequence stars.

Clark, Frank O.↗
NASA NTRS1993

The fate of captured gas: NGC 3077 and star formation in the M81 system

NGC 3077 is the third largest system in the M81 swarm of galaxies, after the giant spiral M81 itself and dwarf oddity M82. We are interested in exploring the fate of molecular material in NGC 3077. For that reason we have mapped the distribution of J = 1 to 0 CO emission in the central approximately 1 arcmin (1 kpc) diameter region of the galaxy using the Owens Valley millimeter-array with an angular resolution of 6.'7 x 5.'7 (110 pc x 90 pc). The results are shown on the following page as a series of velocity channel maps with delta v = 13 km s(exp -1).

Thronson, Harley A., Jr.↗
NASA NTRS1992

On the molecular complexity of the hot cores in Orion A - Grain surface chemistry as 'The last refuge of the scoundrel'

We have modeled the gas phase chemistry of warm molecular material around protostars that is seeded with evaporating grain mantles. We show that the release of simple molecules into the gas drives ion-molecule and neutral chemistries which can account for many of the complex O-bearing and N-bearing molecules observed in hot cores. Initial grain mantle components and secondary product molecules are identified, and the observational consequences are discussed.

Charnley, S. B.↗
NASA NTRS1993

Detection of boron, cobalt, and other weak interstellar lines toward Zeta Ophiuchi

Numerous weak lines from interstellar atomic species toward Zeta Ophiuchi were observed with the Goddard High-Resolution Spectrograph. Of particular note are the first interstellar detection of cobalt and the detection of boron in this sight line. These measurements provide estimates for the amount of depletion for the two elements. Boron, a volatile, and cobalt, a refractory element, display the depletion pattern found by Savage et al. (1992). The abundance of phosphorus in the H II region associated with the star was obtained from a detection of P III. Additional weak lines from S I, C I, Ni II, and Cu II were detected for the first time; these lines provide the basis for refinements in oscillator strength and column density. Analysis of the neutral sulfur data indicates that the atomic gas is more widely distributed than the molecular material in the main component.

Federman, S. R.↗