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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Conveyor-belt magneto-optical trapping of molecules

Abstract Laser cooling is used to produce ultracold atoms and molecules for quantum science and precision measurement applications. Molecules are more challenging to cool than atoms due to their vibrational and rotational internal degrees of freedom. Molecular rotations lead to the use of type-II transitions ( F ⩾ F ′ ) for magneto-optical trapping (MOT). When typical red detuned light frequencies are applied to these transitions, sub-Doppler heating is induced, resulting in higher temperatures and larger molecular cloud sizes than realized with the type-I MOTs most often used with atoms. To improve type-II MOTs, Jarvis et al (2018 Phys. Rev. Lett. 120 083201) proposed a blue-detuned MOT to be applied after initial cooling and capture with a red-detuned MOT. This was successfully implemented (Burau et al 2023 Phys. Rev. Lett. 130 193401; Jorapur et al 2024 Phys. Rev. Lett. 132 163403; Li et al 2024 Phys. Rev. Lett. 132 233402), realizing colder and denser molecular samples. Very recently, Hallas et al (2024 arXiv:2404.03636) demonstrated a blue-detuned MOT with a ‘1+2’ configuration that resulted in even stronger compression of the molecular cloud. Here, we describe and characterize theoretically the conveyor-belt mechanism that underlies this observed enhanced compression. We perform numerical simulations of the conveyor-belt mechanism using both stochastic Schrödinger equation and optical Bloch equation approaches. We investigate the conveyor-belt MOT characteristics in relation to laser parameters, g -factors and the structure of the molecule, and find that conveyor-belt trapping should be applicable to a wide range of laser-coolable molecules.

Li, Grace K. (ORCID:0000000277223355)↗
DOE OSTI2024

Chemical reaction enhanced graph learning for molecule representation

Abstract Motivation Molecular representation learning (MRL) models molecules with low-dimensional vectors to support biological and chemical applications. Current methods primarily rely on intrinsic molecular information to learn molecular representations, but they often overlook effectively integrating domain knowledge into MRL. Results In this article, we develop a reaction-enhanced graph learning (RXGL) framework for MRL, utilizing chemical reactions as domain knowledge. RXGL introduces dual graph learning modules to model molecule representation. One module employs graph convolutions on molecular graphs to capture molecule structures. The other module constructs a reaction-aware graph from chemical reactions and designs a novel graph attention network on this graph to integrate reaction-level relations into molecular modeling. To refine molecule representations, we design a reaction-based relation learning task, which considers the relations between the reactant and product sides in reactions. In addition, we introduce a cross-view contrastive task to strengthen the cooperative associations between molecular and reaction-aware graph learning. Experiment results show that our RXGL achieves strong performance in various downstream tasks, including product prediction, reaction classification, and molecular property prediction. Availability and implementation The code is publicly available at https://github.com/coder-ACAC/RLM.

Biochemistry & Molecular Biology↗
DOE OSTI2024

Photoinitiated Reactions of Molecules and Radicals in Molecular Beams

The UV photochemistry of organic molecules is a fundamental process that governs reactions in the atmosphere, synthetic chemistry, processing of organic aerosols, and biological damage in living tissues. In many organic molecules, the ensuing evolution involves pathways that are in competition, giving rise to different products, isomerization, coupling to other electronic states, and secondary reactive collisions. Because photodissociation is usually fast (picoseconds to microseconds), these processes are far from equilibrium and are controlled by kinetic competition and dynamical forces. The work accomplished was focused primarily on the photochemistry of alpha-keto carboxylic acids, a group of acids produced from natural sources, which are implicated in aerosol formation and biological processes. In the atmosphere, they are destroyed mainly by solar radiation. Studying their photochemistry has been surprisingly difficult because of the complexity of their excited electronic states, and the effect of collisions and secondary reactions. The second project investigated the lifetime of excited electronic states of pyrazine and picoline and had both experimental and theoretical aspects. The work focused on a model molecule, pyruvic acid (PA), because it was hypothesized that it should be a good source of the unstable carbene, methylhydroxycarbene (MHC). PA has an internal hydrogen bond that controls the evolution of its decomposition. The decomposition was studied following excitation to two of its lowest excited states reached by laser irradiation at 351 and 193 nm. The photodissociation dynamics in the absence and presence of collisions was monitored and compared. Understanding the UV photochemistry requires the use of complementary experimental approaches. Two methods were enlisted, which together generated a comprehensive and detailed set of results: (i) The time-sliced velocity map imaging (SVMI) instrument at USC was exploited to determine kinetic energy release of fragments, fast dissociation timescales, and internal state distributions of fragments for which Resonance Enhanced Multiphoton Ionization (REMPI) schemes exist; and (ii) The multiplexed photoionization mass spectrometer (MPIMS) setup developed at the Sandia Combustion Research Facility was used for product discovery, achieved by exploiting tunable narrowband VUV radiation at the Advanced Light Source (ALS), and to follow in real time their subsequent unimolecular and bimolecular reactions. The experimental conditions ranged from collisionless molecular beams to study nascent products to flow reactors of variable pressures to study subsequent bimolecular reactions of the products. The goals stated above were successfully accomplished. By exciting PA to its lowest excited state, MHC was identified as the only primary product and its isomerization to vinylalcohol and acetaldehyde was directly observed in real time. Moreover, we reported the first bimolecular reaction of MHC, which was with acetaldehyde, and identified its reaction product. This paves the way for the study of other reactions of this important carbene intermediate. When excitation was carried out at 193 nm, which imparted much higher energy to PA, many more products were directly observed in real time, some deriving from three-body dissociation. Quantitative branching ratios and secondary reactions of radical products were also determined and analyzed. The studies of pyrazine and picoline focused on the second excited state of these molecules and showed (via ionization studies) that their excited states were very short lived (<100 fs) because of efficient couplings to lower electronic states via vibronic coupling. Theoretical work on modeling the absorption spectrum and decay mechanisms of the excited states are in progress in collaboration with theoreticians.

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

Omics-Based Comparison of Fungal Virulence Genes, Biosynthetic Gene Clusters, and Small Molecules in Penicillium expansum and Penicillium chrysogenum

Penicillium expansum is a ubiquitous pathogenic fungus that causes blue mold decay of apple fruit postharvest, and another member of the genus, Penicillium chrysogenum, is a well-studied saprophyte valued for antibiotic and small molecule production. While these two fungi have been investigated individually, a recent discovery revealed that P. chrysogenum can block P. expansum-mediated decay of apple fruit. To shed light on this observation, we conducted a comparative genomic, transcriptomic, and metabolomic study of two P. chrysogenum (404 and 413) and two P. expansum (Pe21 and R19) isolates. Global transcriptional and metabolomic outputs were disparate between the species, nearly identical for P. chrysogenum isolates, and different between P. expansum isolates. Further, the two P. chrysogenum genomes revealed secondary metabolite gene clusters that varied widely from P. expansum. This included the absence of an intact patulin gene cluster in P. chrysogenum, which corroborates the metabolomic data regarding its inability to produce patulin. Additionally, a core subset of P. expansum virulence gene homologues were identified in P. chrysogenum and were similarly transcriptionally regulated in vitro. Molecules with varying biological activities, and phytohormone-like compounds were detected for the first time in P. expansum while antibiotics like penicillin G and other biologically active molecules were discovered in P. chrysogenum culture supernatants. Our findings provide a solid omics-based foundation of small molecule production in these two fungal species with implications in postharvest context and expand the current knowledge of the Penicillium-derived chemical repertoire for broader fundamental and practical applications.

Bartholomew, Holly P. (ORCID:0000000292726399)↗
NASA NTRS1971

Opacity probability distribution functions for electronic systems of CN and C2 molecules including their stellar isotopic forms.

The basis and techniques are presented for generating opacity probability distribution functions for the CN molecule (red and violet systems) and the C2 molecule (Swan, Phillips, Ballik-Ramsay systems), two of the more important diatomic molecules in the spectra of carbon stars, with a view to including these distribution functions in equilibrium model atmosphere calculations. Comparisons to the CO molecule are also shown. T he computation of the monochromatic absorption coefficient uses the most recent molecular data with revision of the oscillator strengths for some of the band systems. The total molecular stellar mass absorption coefficient is established through fifteen equations of molecular dissociation equilibrium to relate the distribution functions to each other on a per gram of stellar material basis.

Querci, F.↗
NASA NTRS1973

Photochemistry of interstellar molecules

The role of photochemistry in determining the lifetime of interstellar molecules is considered. The probability of photodecomposition depends on three factors, including the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. A more detailed discussion of the photochemistry of five molecules is presented, giving attention to carbonyl sulfide, methyl acetylene, nitric oxide, acetylene, and benzene. Lifetimes of interstellar molecules in unobscured regions are in the range from 5 to 100 years. It is concluded that polyatomic molecules can exist only in dense clouds which protect them from the full interstellar radiation field.

Stief, L. J.↗
NASA NTRS1976

Infrared spectra of molecules and materials of astrophysical interest

The vibrational spectra from 4,000 to 33/cm of several molecules which may be present in the atmosphere of the Jovian planets or exist in outer space were studied. These studies have been made to provide vibrational frequencies which can be used to: (1) determine the composition of the cloud covers of several of the planets, (2) provide structural information under favorable circumstances, (3) provide necessary data from which accurate thermodynamic data can be calculated, and (4) furnish information as to the nature of the potential energy function of the molecules and forces acting within them. Some of the molecules studied can be produced photochemically from methane, ammonia, and hydrogen sulfide which are thought to be constituents of the planets with reducing atmospheres. Some of the compounds will polymerize under ultraviolet radiation and drop out of the atmospheres. However, planets with a hot base, like that of Jupiter, may rebuild molecules destroyed photochemically. These criteria were used in selecting the compounds under study.

Durig, J. R.↗
NASA NTRS1976

Measurement and significance of the equilibrium reaction C-13/+/ + /C-12/O yields C-12/+/ + /C-13/O for alteration of the C-13/C-12 ratio in interstellar molecules

Laboratory measurements using the ion-cyclotron resonance technique yield a rate constant of 2 by 10 to the -10th power cu cm/sec at 300 K for the isotope exchange C-13(+) + (C-12)O yields C-12(+) + (C-13)O. According to the usual ideas about ion-molecule reactions, this rate constant should also be appropriate at temperatures not exceeding about 100 K. Then the observed C-13/C-12 ratio obtained from radio observation of interstellar molecules may be either larger or smaller than the actual value in the interstellar medium by factors of 2 or so. If the ratio is altered from the actual interstellar value, it will not be the same in all molecules, and CO will tend to have the highest value. The chief astronomical uncertainty for the occurrence of this isotope fractionation is the abundance of 'unobservable' molecules which can react rapidly with C(+): e.g., O2, H2O, CO2, and CH4. If their abundance is greater than about one-tenth that of CO, the isotope fractionation will be inhibited.

Watson, W. D.↗
NASA NTRS1976

Vibration-translation energy transfer in vibrationally excited diatomic molecules

A semiclassical collision model is applied to the study of energy transfer rates between a vibrationally excited diatomic molecule and a structureless atom. The molecule is modeled as an anharmonic oscillator with a multitude of dynamically coupled vibrational states. Three main aspects in the prediction of vibrational energy transfer rates are considered. The applicability of the semiclassical model to an anharmonic oscillator is first evaluated for collinear encounters. Second, the collinear semiclassical model is applied to obtain numerical predictions of the vibrational energy transfer rate dependence on the initial vibrational state quantum number. Thermally averaged vibration-translation rate coefficients are predicted and compared with CO-He experimental values for both ground and excited initial states. The numerical model is also used as a basis for evaluating several less complete but analytic models. Third, the role of rational motion in the dynamics of vibrational energy transfer is examined. A three-dimensional semiclassical collision model is constructed with coupled rotational motion included. Energy transfer within the molecule is shown to be dominated by vibration-rotation transitions with small changes in angular momentum. The rates of vibrational energy transfer in molecules with rational frequencies that are very small in comparison to their vibrational frequency are shown to be adequately treated by the preceding collinear models.

Mckenzie, R. L.↗
NASA NTRS1979

Molecules of significance in planetary aeronomy

This monograph is basically devoted to spectroscopic information of the molecules of planetary interest. Only those molecules have been dealt with which have been confirmed spectroscopically to be present in the atmosphere of major planets of our solar system and play an important role in the aeronomy of the respective planets. An introduction giving the general conditions of planets and their atmospheres including the gaseous molecules is given. Some typical planetary spectra is presented and supported with a discussion on some basic concepts of optical absorption and molecular parameters that are important to the study of planetary atmospheres. Quantities like dipole moments, transition probabilities, Einstein coefficients and line strengths, radiative life times, absorption cross sections, oscillator strengths, line widths and profiles, equivalent widths, growth curves, bond strengths, electronic transition moments, Franck-Condon factors and r-centroids, etc., are discussed. Spectroscopic information and relevant data of 6 diatomic (HF, HCL, CO, H2, O2, N2) and 6 polyatomic (CO2, N2), O3, HeO, NH3, CH4) molecules are presented.

Mohan, H.↗
NASA NTRS1979

Long chain carbon molecules and diffuse interstellar lines

An estimate of the abundances of chain hydrocarbon molecules expected in dense interstellar clouds as a result of gas-phase chemistry alone supports the hypothesis that the long chain molecules are responsible for the diffuse interstellar lines seen in the optical spectra of stars lying behind fairly low-density interstellar clouds. In particular, it is shown that the equilibrium abundances of the long chain carbon molecules may remain quite high even for molecules with as many as 11 carbon atoms.

Mitchell, G. F.↗
NASA NTRS1980

Molecule formation and infrared emission in fast interstellar shocks. II - Dissociation speeds for interstellar shock waves

The postshock destruction of molecules is examined, including the processes of (1) collisions with neutral hydrogen atoms and molecules, (2) electronic collisions, and (3) neutral chemical reactions with atoms, particularly atomic hydrogen. By using conservative estimates of collisional dissociation rates from individual vibrational states, it is found that process (1) leads to the destruction of molecular hydrogen behind shocks with speeds equal to or greater than 25 km/s if the preshock molecular gas has hydrogen nucleus densities of equal to or greater than 10 to the 4th/cu cm. At lower densities (100 per cu cm), destruction occurs for shock speeds equal to or greater than 50 km/s and process (2) dominates. Dissociation of molecules such as CO, H2O, and O2 follows the destruction of H2, as the resultant hydrogen atoms chemically dissociate the metal atoms from their bonds (process 3) in the hot postshock gas. These results demonstrate that many of the observed high-speed interstellar molecules, if shock accelerated, must have dissociated and reformed in the postshock gas.

Hollenbach, D.↗
NASA NTRS1981

Three new 'nonterrestrial' molecules

Eight new interstellar lines have been detected from three molecules not previously observed spectroscopically in space or in the laboratory. One is a linear or nearly linear molecule with microwave constants B0 equals 21,337.15 plus or minus 0.06 MHz, D0 equals 21.4 plus or minus 1.5 kHz. This is the thioformyl ion HCS(plus), first identified because B0 and D0 are close to those calculated, and now confirmed by laboratory detection of one of the present lines (Gudeman et al.). The second molecule, also linear or nearly so, has microwave constants B0 equals 10,691,406 plus or minus 0.043 MHz, D0 equals 1.84 plus or minus 0.91 kHz close to those expected for the isoelectronic systems HOCO(plus) and HOCN; a choice between the two cannot be made on the basis of the available astronomical data. The existence of a third molecule is deduced from an unidentified line at 85,338 MHz that has been found in many sources, is fairly intense in several, and may be self-absorbed in Sgr B2.

Thaddeus, P.↗
NASA NTRS1987

Observations of molecules in comets

Ultraviolet and visible spectroscopy of comets has identified a large number of species in the coma, most of which appear to be the photodissociation and photoionization products of the 'parent' molecules evaporated directly from the cometary nucleus. Analyses of cometary spectra support the icy conglomerate model of the nucleus with H2O as the dominant ice species. Two molecules detected in the ultraviolet, CO and S2, are of particular interest to the study of the cosmogonic evolution of cometary grains. CO appears to be a highly variable constituent from comet to comet, while S2, first observed in comet IRAS-Araki-Alcock in 1983, is found in no other celestial source. Both of these molecules appear to be parent molecules.

Feldman, P. D.↗
NASA NTRS1988

Large molecules in diffuse interstellar clouds

The effects of the presence of a substantial component of large molecules on the chemistry of diffuse molecular clouds are explored, and detailed models of the zeta Persei and zeta Ophiuchi clouds are constructed. The major consequence is a reduction in the abundances of singly charged atomic species. The long-standing discrepancy between cloud densities inferred from rotational and fine-structure level populations and from the ionization balance can be resolved by postulating a fractional abundance of large molecules of 1 x 10 to the -7th for zeta Persei and 6 x 10 to the -7th for zeta Ophiuchi. If the large molecules are polycyclic aromatic hydrocarbons (PAH) containing about 50 carbon atoms, they contain 1 percent of the carbon in zeta Persei and 7 percent in zeta Ophiuchi. Other consequences of the possible presence of PAH molecules are discussed.

Lepp, S.↗
NASA NTRS1991

Photoabsorption and photodissociation of molecules important in the interstellar medium

The photoabsorption, photodissociation, and fluorescence cross sections of interstellar molecules are measured at 90 to 250 nm. These quantitative optical data are needed for the understanding of the formation and destruction processes of molecules under the intense interstellar UV radiation field. Research covering the following topics is presented: (1) fluorescences from photoexcitation of CH4, CH3OH, and CH3SH; (2) NO gamma emission from photoexcitation of NO; (3) photoexcitation cross sections of aromatic molecules; (4) IR emission from UV excitation of HONO2; (5) IR emission from UV excitation of benzene and methyl-derivitives; and (6) IR emission from UV excitation of polycyclic aromatic hydrocarbon molecules.

Lee, Long C.↗
NASA NTRS1991

The formation of molecules in protostellar winds

The production and destruction processes for molecules in very fast protostellar winds are analyzed and modeled with a one-dimensional chemical kinetics code. Radial density and temperature distributions suggested by protostellar theory are explored as are a range of mass-loss rates. The efficiency of in situ formation of heavy molecules is found to be high if the wind temperature falls sufficiently rapidly, as indicated by theory. The degree of molecular conversion is a strong function of the mass-loss rate and of density gradients associated with the acceleration and collimation of the wind. Even in cases where essentially all of the heavy atoms are processed into molecules, a significant fraction of atomic hydrogen remains so that hghly molecular, protostellar winds are able to emit the 21-cm line. Although CO has a substantial abundance in most models relevant to very young protostars, high abundances of other molecules such as SiO and H2O signify more complete association characteristic of winds containing regions of very high density. Although the models apply only to regions close to the protostar, they are in qualitative accord with recent observations at much larger distances of both atomic and molecular emission from extremely high-velocity flow.

Glassgold, A. E.↗