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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
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 NTRS1997

Data Base for CFD Validation

The flow behind the shock wave formed around objects which fly at hypervelocity behaves differently from that of a perfect gas. Molecules become vibrationally excited, dissociated, and ionized. The hot gas may emit or absorb radiation. When the atoms produced by dissociation reach the wall surface, chemical reactions, including recombination, may occur. The thermochemical phenomena of vibration, dissociation, ionization, surface chemical reaction, and radiation are referred to commonly as high-temperature real-gas phenomena. The phenomena cause changes in the dynamic behavior of the flow and the surface pressure and heat transfer distribution around the object. The character of a real gas is described by the internal degrees of freedom and state of constituent molecules; nitrogen and oxygen for air. The internal energy states, rotation, vibration and electronic, of the molecules are excited and, in the limit, the molecular bonds are exceeded and the gas dissociated into atomic and, possibly, ionic constituents. The process of energy transfer causing excitation, dissociation and recombination is a rate process controlled by particle collisions. Binary, two-body, collisions are sufficient to cause internal excitation, dissociation and ionization while three-body collisions are required to recombine the particles into molecular constituents. If the rates of energy transfer are fast with respect to the local fluid dynamic time scale the gas is in, or nearly in, equilibrium. If the energy transfer rates are very slow the gas can be described as frozen. In all other instances, wherein any of the energy exchange rates are comparable to the local fluid time scale, the gas will be thermally or chemically reacting and out of equilibrium. Real gas thermochemical nonequilibrium processes are important in the determination of aerodynamic heating; both convective (including wall catalytic effects) and radiative heating. To illustrate this we consider the hypervelocity flow over a bluff body typical of an atmospheric entry vehicle or an aerospace transfer vehicle (ASTV). The qualitative aspects of a hypersonic flow field over a bluff body are discussed in two parts, forebody and afterbody, with attention to which particular physical effects must be included in an analysis. This will indicate what type of numerical modeling will be adequate in each region of the flow. A bluff forebody flow field is dominated by the presence of the strong bow shock wave and the consequent heating, and chemical reaction of the gas. At high altitude hypersonic flight conditions the thermal excitation and chemical reaction of the gas occur slowly enough that a significant portion of the flow field is in a state of thermochemical nonequilibrium. A second important effect is the presence of the thick boundary layer along the forebody surface. In this region there are large thermal and chemical species gradients due to the interaction of the gas with the wall. Also at high altitudes the shock wave and the boundary layer may become so thick that they merge; in this case the entire shock layer is dominated by viscous effects.

Deiwert, George S.↗
NASA NTRS1994

A Search for Structure in PAH Emission in Extended Sources at 3.3 and 3.4 Microns

We have observed three extended sources of the infrared emission features associated with polycyclic aromatic hydrocarbons (PAHs), using a 128x128 InSb array mounted on the 1.5 m NASA/Steward telescope on Mt. Lemmon. We used a CVF (1.5% bandpass) to isolate the emission from the 3.29 and 3.40 microns PAH features in NGC 1333 #3, Sharpless 106, and the Orion Bar. In all three sources, the 3.29 and 3.40 microns emission features arise from the same regions, but show decidedly different structure. We are analyzing the images to determine the relationship of the 3.40 microns feature to the main feature at 3.29 microns. The 3.40 microns feature may be a vibrational overtone of the 3.29 microns feature, or it may arise from attached molecular sidegroups.

Bregman, Jesse↗
NASA NTRS1996

Ab Initio Calculation of Accurate Vibrational Frequencies for Molecules of Interest in Atmospheric Chemistry

Due to advances in quantum mechanical methods over the last few years, it is now possible to determine ab initio potential energy surfaces in which fundamental vibrational frequencies are accurate to within +/- 8 cm(sup -1) on average, and molecular bond distances are accurate to within +/- 0.001-0.003 A, depending on the nature of the bond. That is, the potential energy surfaces have not been scaled or empirically adjusted in any way, showing that theoretical methods have progressed to the point of being useful in analyzing spectra that are not from a tightly controlled laboratory environment, such as rovibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy win be presented and discussed. These include the HNO, CH4, C2H4, and ClCN molecules. The HNO molecule is interesting due to the very large H-N anharmonicity, while ClCN has a very large Fermi resonance. The ab initio studies for the CH4 and C2H4 molecules present the first accurate full quartic force fields of any kind (i.e., whether theoretical or empirical) for a five-atom and six-atom system, respectively.

Lee, Timothy J.↗
DOE OSTI2020

Caught in the H inact : Crystal Structure and Spectroscopy Reveal a Sulfur Bound to the Active Site of an O 2 -stable State of [FeFe] Hydrogenase

[FeFe] hydrogenases are the most active H 2 converting catalysts in nature, but their extreme oxygen sensitivity limits their use in technological applications. The [FeFe] hydrogenases from sulfate reducing bacteria can be purified in an O 2 -stable state called H inact . To date, the structure and mechanism of formation of H inact remain unknown. Our 1.65 Å crystal structure of this state reveals a sulfur ligand bound to the open coordination site. Furthermore, in-depth spectroscopic characterization by X-ray absorption spectroscopy (XAS), nuclear resonance vibrational spectroscopy (NRVS), resonance Raman (RR) spectroscopy and infrared (IR) spectroscopy, together with hybrid quantum mechanical and molecular mechanical (QM/MM) calculations, provide detailed chemical insight into the Hinact state and its mechanism of formation. This may facilitate the design of O 2 -stable hydrogenases and molecular catalysts.

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

Physicochemical control of solvation and molecular assembly of charged amphiphilic oligomers at air-aqueous interfaces

Hypothesis : Understanding the rules that control the assembly of nanostructured soft materials at interfaces is central to many applications. We hypothesize that electrolytes can be used to alter the hydration shell of amphiphilic oligomers at the air-aqueous interface of Langmuir films, thereby providing a means to control the formation of emergent nanostructures. Experiments : Three representative salts – (NaF, NaCl, NaSCN) were studied for mediating the self-assembly of oligodimethylsiloxane methylimidazolium (ODMS-MIM + ) amphiphiles in Langmuir films. The effects of the different salts on the nanostructure assembly of these films were probed using vibrational sum frequency generation (SFG) spectroscopy and Langmuir trough techniques. Experimental data were supported by atomistic molecular dynamic simulations. Findings : Langmuir trough surface pressure – area isotherms suggested a surprising effect on oligomer assembly, whereby the presence of anions affects the stability of the interfacial layer irrespective of their surface propensities. In contrast, SFG results implied a strong anion effect that parallels the surface activity of anions. These seemingly contradictory trends are explained by anion driven tail dehydration resulting in increasingly heterogeneous systems with entangled ODMS tails and appreciable anion penetration into the complex interfacial layer comprised of headgroups, tails, and interfacial water molecules. These findings provide physical and chemical insight for tuning a wide range of interfacial assemblies.

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

Anharmonic phonons, thermal expansion, and nuclear quantum effects in Zn

The anharmonic behavior of phonons and thermal expansion of hexagonal zinc were studied from 15 to 690 K by inelastic neutron scattering (INS) and ab initio simulations. Phonon spectra were measured for Q-points covering the full Brillouin zone, giving the phonon density of states (DOS) and dispersions along high-symmetry directions. The dispersions were sharp at 15 K, but diffuse intensity was observed at energies above them. The dispersions broadened with temperature T and the diffuse intensity became stronger. This diffuse intensity appeared in all INS measurements and simulations, except for classical molecular dynamics at 15 K. The temperature-dependent effective potential (TDEP) method, which included the nuclear quantum effect from zero-point vibrational dynamics, was used to calculate the free energy and thermal expansion. For T < 100 K nuclear quantum effects were important for obtaining the correct negative thermal expansion, and path integral molecular dynamics (PIMD) was particularly effective for obtaining the negative thermal expansion in the basal plane. A Heisenberg-Langevin model for interacting phonons coupled to a thermal bath was able to reproduce the shape and intensity of the diffuse spectral features.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2004

Formation and Destruction Processes of Interstellar Dust: From Organic Molecules to carbonaceous Grains

The study of the formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. interstellar dust presents a continuous size distribution from large molecules, radicals and ions to nanometer-sized particles to micron-sized grains. The lower end of the dust size distribution is thought to be responsible for the ubiquitous spectral features that are seen in emission in the IR (UIBs) and in absorption in the visible (DIBs). The higher end of the dust-size distribution is thought to be responsible for the continuum emission plateau that is seen in the IR and for the strong absorption seen in the interstellar UV extinction curve. All these spectral signatures are characteristic of cosmic organic materials that are ubiquitous and present in various forms from gas-phase molecules to solid-state grains. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of dust. Recent space observations in the UV (HST) and in the IR (ISO) help place size constraints on the molecular component of carbonaceous IS dust and indicate that small (ie., subnanometer) PAHs cannot contribute significantly to the IS features in the UV and in the IR. Studies of large molecular and nano-sized IS dust analogs formed from PAH precursors have been performed in our laboratory under conditions that simulate diffuse ISM environments (the particles are cold -100 K vibrational energy, isolated in the gas phase and exposed to a high-energy discharge environment in a cold plasma). The species (molecules, molecular fragments, ions, nanoparticles, etc) formed in the pulsed discharge nozzle (PDN) plasma source are detected with a high-sensitivity cavity ring-down spectrometer (CRDS). We will present new experimental results that indicate that nanoparticles are generated in the plasma. From these unique measurements, we derive information on the nature, the size and the structure of interstellar dust particles, the growth and the destruction processes of IS dust and the resulting budget of extraterrestrial organic molecules.

Salama, F.↗
NASA NTRS1985

Molecular spectroscopy from the Kuiper Airborne Observatory

Interstellar and circumstellar molecules are investigated through medium-resolution infrared spectrosocpy of the vibration-rotation and pure rotational transitions. A primary goal was the construction and improvement of instrumentation for the near and middle infrared regions, wavelengths between 2 and 10 microns. The main instrument was a cooled grating spectrometer with an interchangeable detector focal plane which could be used on the Kuiper Airborne Observatory (KAO) for airborne observations, and also at ground-based facilities. Interstellar shock waves were investigated by H2 emission from the Orion Nebula, W51, and the proto-planetary nebulae CRL 2688 and CRL 618. The observations determined the physical conditions in shocked molecular gas near these objects. From these it was possible to characterize the energetic history of mass loss from both pre- and post-main sequence stars in the regions.

Beckwith, S.↗
NASA NTRS1981

The possibility of vibrational lasing in CD3F

A new lasing mechanism is proposed as a result of the unusual performance characteristics of the 206 micron emission of the CD3F optically pumped molecular laser. The scheme presented is only meant to be suggestive. It is pointed out that most of the CD3F lines are pure rotational. However, the three lines at 206, 201.5, and 247.5 microns are seen as indicating the possibility of vibrational lasing. The 247.5 micron line is thought to be the most likely other candidate of the remaining two. This conclusion derives from the availability of pump power in the 9R10 CO2 laser line vis a vis the strong emission and 0.20 torr optimum operating pressure.

Lawandy, N. M.↗
DOE OSTI2021

Simulations of the IR and Raman spectra of water confined in amorphous silica slit pores

Water in nano-scale confining environments is a key element in many biological, material, and geological systems. The structure and dynamics of the liquid can be dramatically modified under these conditions. Probing these changes can be challenging, but vibrational spectroscopy has emerged as a powerful tool for investigating their behavior. A critical, evolving component of this approach is a detailed understanding of the connection between spectroscopic features and molecular-level details. In this paper, this issue is addressed by using molecular dynamics simulations to simulate the linear infrared (IR) and Raman spectra for isotopically dilute HOD in D 2 O confined in hydroxylated amorphous silica slit pores. The effect of slit-pore width and hydroxyl density on the silica surface on the vibrational spectra is also investigated. The primary effect of confinement is a blueshift in the frequency of OH groups donating a hydrogen bond to the silica surface. This appears as a slight shift in the total (measurable) spectra but is clearly seen in the distance-based IR and Raman spectra. Analysis indicates that these changes upon confinement are associated with the weaker hydrogen-bond accepting properties of silica oxygens compared to water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Debye-Waller factor of disordered solids: The case for amorphous silicon

This paper presents a first-principles study of the Debye-Waller factor and the Debye temperature for amorphous silicon (α-Si) from lattice-dynamical calculations and direct molecular-dynamics simulations using density-functional theory (DFT). The effects of temperature and structural disorder on the intensity of the diffraction maxima and the vibrational mean-square displacement (MSD) of Si atoms are studied in the harmonic approximation, with particular emphasis on the bond-length disorder, the presence of coordination defects, and microvoids in α-Si networks. It has been observed that the MSDs associated with tetrahedrally bonded Si atoms are considerably lower than their dangling-bond counterparts—originating from isolated and vacancy-induced clustered defects—and those on the surface of microvoids, leading to an asymmetric non-Gaussian tail in the distribution of atomic displacements. An examination of the effect of anharmonicity on the MSD at high temperatures using direct ab initio molecular-dynamics simulations (without the harmonic approximation) suggests that the vibrational motion in α-Si is practically unaffected by anharmonic effects at temperatures below 400 K, as far as the present DFT calculations are concerned. The Debye temperature of α-Si is found to be in the range of 488–541 K from specific-heat and MSD calculations using first-principles lattice-dynamical calculations in the harmonic approximation, which matches closely with the experimental value of 487–528 K obtained from specific-heat measurements of α-Si at low temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Ab initio studies of the impact of the Debye-Waller factor on the structural and dynamical properties of amorphous semiconductors: The case of a-Si

This paper presents a first-principles study of the Debye-Waller factor and the Debye temperature for amorphous silicon (a-Si) from lattice-dynamical calculations and direct molecular-dynamics simulations using density-functional theory (DFT). The effects of temperature and structural disorder on the intensity of the diffraction maxima and the vibrational mean-square displacement (MSD) of Si atoms are studied in the harmonic approximation, with particular emphasis on the bond-length disorder, the presence of coordination defects, and microvoids in a-Si networks. It has been observed that the MSDs associated with tetrahedrally-bonded Si atoms are considerably lower than their dangling-bond counterparts – originating from isolated and vacancy-induced clustered defects – and those on the surface of microvoids, leading to an asymmetric non-gaussian tail in the distribution of atomic displacements. An examination of the effect of anharmonicity on the MSD at high temperatures using direct ab initio molecular-dynamics simulations (without the harmonic approximation) suggests that the vibrational motion in a-Si is practically unaffected by anharmonic effects at temperatures below 400 K, as far as the present DFT calculations are concerned. The Debye temperature of a-Si is found to be in the range of 488–541 K from specific-heat and MSD calculations using first-principles lattice-dynamical calculations in the harmonic approximation, which matches closely with the experimental value of 487–528 K obtained from specific-heat measurements of a-Si at low temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

La 3+ and Y 3+ interactions with the carboxylic acid moiety at the liquid/vapor interface: Identification of binding complexes, charge reversal, and detection limits

Specific interactions of yttrium and lanthanum ions with a fatty acid Langmuir monolayer were investigated using vibrational sum frequency spectroscopy. The trivalent ions were shown to interact with the charged form of the carboxylic acid group from nanomolar concentrations (<300 nM). Analysis of the spectral features from both the symmetric and the asymmetric carboxylate modes reveals the presence of at least three distinct coordination structures linked to specific binding configurations. Although the same species were identified for both La 3+ and Y 3+ , they display a different concentration dependence, highlighting the ion-specificity of the interaction. From the analysis of the response of interfacial water molecules, the reversal of the surface charge, as well as the formation of yttrium hydroxide complexes, were detected upon increasing the amount of salt in solution. The binding interaction and kinetics of absorption are sensitive to the solution pH, showing a distinct ion speciation in the interfacial region when compared to the bulk. Changing the subphase pH or adding a monovalent background electrolyte that promotes deprotonation of the carboxylic acid headgroup could further improve the detection limit of La 3+ and Y 3+ to concentrations < 100 nM. These findings demonstrate that nM concentrations of trace metals contaminants, typically found on monovalent salts, can significantly influence the binding structure and kinetics in Langmuir monolayers.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1974

Molecular absorption parameters in atmospheric modelling

Molecular spectroscopic parameters are compiled for a number of infrared-active molecules occurring naturally in the terrestrial atmosphere. The following molecules are included in this compilation: water vapor; carbon dioxide; ozone; nitrous oxide; carbon monoxide; methane; and oxygen. The spectral region covered extends from less than 1 micron to the far infrared, and data are presented on more than 100,000 spectral lines. The parameters included in the compilation for each line are: frequency, intensity, half-width, energy of the lower state of the transition, vibrational and rotational identifications of the upper and lower energy states, an isotopic identification, and a molecular identification. Using this data compilation, band model parameters are presented for water vapor, carbon dioxide, and ozone averaged over 20 wavenumber intervals. Using these parameters in a random model formulation, transmittance spectra are provided and compared with both degraded monochromatic calculations and laboratory data.

Mcclatchey, R. A.↗
DOE OSTI2024

Measurement of coherent vibrational dynamics with X-ray Transient Absorption Spectroscopy simultaneously at the Carbon K- and Chlorine L 2,3 - edges

X-ray Transient Absorption Spectroscopy (XTAS) is a powerful probe for ultrafast molecular dynamics. The evolution of XTAS signal is controlled by the shapes of potential energy surfaces of the associated core-excited states, which are difficult to directly measure. Here, we study the vibrational dynamics of Raman activated CCl 4 with XTAS targeting the C 1s and Cl 2p electrons. The totally symmetric stretching mode leads to concerted elongation or contraction in bond lengths, which in turn induce an experimentally measurable red or blue shift in the X-ray absorption energies associated with inner-shell electron excitations to the valence antibonding levels. The ratios between slopes of different core-excited potential energy surfaces (CEPESs) thereby extracted agree very well with Restricted Open-Shell Kohn-Sham calculations. The other, asymmetric, modes do not measurably contribute to the XTAS signal. The results highlight the ability of XTAS to reveal coherent nuclear dynamics involving < 0.01 Å atomic displacements and also provide direct measurement of forces on CEPESs.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1992

An extensive ab initio study of the structures, vibrational spectra, quadratic force fields, and relative energetics of three isomers of Cl2O2

Quantum mechanical computational methods are employed for an ab initio investigation of: (1) the molecular properties of the lowest isomers of the ClO dimer; and (2) predicted molecular and thermochemical properties. Techniques employed include electron correlation and particularly singles and doubles coupled-cluster (CCSD) theory with or without perturbational estimates of the effects of connected triple excitations. The isomers ClOClO and ClClO2 are found to have higher energies than the ClOOCl isomer, and the theoretical vibrational frequencies of the isomers are well correlated with experimental data. Experimental values of the heat of formation for the isomers are also compared with calculations based on an isodesmic reaction with Cl2O, H2O, and HOOH.

Lee, Timothy J.↗
DOE OSTI2020

Mode-specific pressure effects on the relaxation of an excited nitromethane molecule in an argon bath

The vibrational and rotational mode-specific relaxations of CH 3 NO 2 with 50 kcal/mol of initial internal energy in an argon bath is computed at 300 K at pressures of 10-400 atm. This work uses archived information from our previously published [J. Chem. Phys. 142, 014303 (2015)] molecular dynamics simulations and employs our previous published [J. Chem. Phys. 151, 034303 (2019)] method for projecting time-dependent Cartesian velocities onto normal mode eigenvectors. The computed relaxations cover three types of energies: vibrational, rotational, and Coriolis. In general, rotational and Coriolis relaxations in all modes are initially fast followed by an orders of magnitude slower relaxation. For all modes, that slower relaxation rate is approximately comparable to the vibrational relaxation rate. For all three types of energies, there are small-scale mode-to-mode variations. Of particular prominence is the exceptionally fast relaxation shared in common by the external rotation about the C-N axis, the internal hindered rotation of the CH 3 group relative to the NO 2 group, and the symmetric stretch of the CH 3 group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗