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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

The Origins of Polycyclic Aromatic Hydrocarbons: Are They Everywhere?

During the past 15 years considerable progress in observational techniques has been achieved in the middle-infrared region (5000-500 per centimeter, 2-20 micron), the region where most diagnostic molecular vibrations occur. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds and others at their edges, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas and solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. The two lectures will focus on the evidence that polycyclic aromatic hydrocarbons (PAHs) are an important, ubiquitous and abundant interstellar species. PAHs are. extremely stable species which can range in size from a few angstroms across to several hundred angstroms (PAHs are also the building blocks of amorphous carbon particles). This identification rests on the suggestive agreement between the laboratory spectra of PAHs with a set of IR emission bands which emanate from many different sources where ultraviolet starlight impinges on a "dusty" region. The picture is that individual PAHs are first pumped into highly vibrationally excited states and relax by fluorescence at their fundamental vibrational frequencies. That PAHs are a ubiquitous interstellar component has serious ramifications in other spectral regions as well, including the strong extinction in the ultraviolet, and the classic visible diffuse interstellar bands discovered more than 50 years ago (but unexplained to this day) The first part of the course will focus on the interpretation of astronomical spectra. The second lecture will start by showing how recent laboratory data on PAHs taken under realistic interstellar conditions has con borated the PAH hypothesis and led to great insight into the conditions in the PAH containing regions. This lecture will end by reviewing the ever-increasing evidence for interstellar PAHs in meteorites and interplanetary dust particles. This in conjunction with the recent suggestion that PAHs are abundant in Jupiter's atmosphere will make the point that "PAHs are Everywhere".

Allamandola, L. J.↗
DOE OSTI2026

Suppressing thermal transport in nonporous polymer hybrids by limiting thermally accessible vibrational modes

Achieving low thermal conductivity in nonporous polymer materials without compromising mechanical integrity remains a longstanding challenge. Conventional strategies, such as introducing porosity, are inherently limited in dense systems. Here, in this study, we demonstrate that thermal transport in polymer–organic filler hybrids is closely associated with the engineered availability of thermally accessible vibrational modes, rather than individual interfacial resistance or porosity. Using PU/organic filler hybrids as a model system, we show that incorporating rigid organic motifs shifts the vibrational density of states toward higher frequencies, where vibrational modes are weakly thermally populated at ambient conditions. This limits the number of heat-carrying channels, leading to suppressed thermal conductivity despite negligible individual interfacial resistance (∼10 −9 m 2 K W −1 ). These findings provide initial evidence that vibrational mode engineering may offer a promising molecular-level route for reducing thermal conductivity in dense polymer–organic hybrid systems.

36 MATERIALS SCIENCE↗
NASA NTRS1984

Structural Analysis of the Support System for a Large Compressor Driven by a Synchronous Electric Motor

For economic reasons, the steam drive for a large compressor was replaced by a large synchronous electric motor. Due to the resulting large increase in mass and because the unit was mounted on a steel frame approximately 18 feet above ground level, it was deemed necessary to determine if a steady state or transient vibration problem existed. There was a definite possibility that a resonant or near resonant condition could be encountered. The ensuing analysis, which led to some structural changes as the analysis proceeded, did not reveal any major steady state vibration problems. However, the analysis did indicate that the system would go through several natural frequencies of the support structure during start-up and shutdown. This led to the development of special start-up and shutdown procedures to minimize the possibility of exciting any of the major structural modes. A coast-down could result in significant support structure and/or equipment damage, especially under certain circumstances. In any event, dynamic field tests verified the major analytical results. The unit has now been operating for over three years without any major vibration problems.

Winter, J. R.↗
DOE OSTI2021

Valence shell photoelectron angular distributions and vibrationally resolved spectra of imidazole: A combined experimental–theoretical study

Linearly polarized synchrotron radiation has been used to record polarization dependent valence shell photoelectron spectra of imidazole in the photon energy range 21–100 eV. These have allowed the photoelectron angular distributions, as characterized by the anisotropy parameter β, and the electronic state intensity branching ratios to be determined. Complementing these experimental data, theoretical photoionization partial cross sections and β-parameters have been calculated for the outer valence shell orbitals. The assignment of the structure appearing in the experimental photoelectron spectra has been guided by vertical ionization energies and spectral intensities calculated by various theoretical methods that incorporate electron correlation and orbital relaxation. Strong orbital relaxation effects have been found for the 15a', nitrogen lone-pair orbital. The calculations also predict that configuration mixing leads to the formation of several low-lying satellite states. The vibrational structure associated with ionization out of a particular orbital has been simulated within the Franck–Condon model using harmonic vibrational modes. The adiabatic approximation appears to be valid for the X 2A" state, with the β-parameter for this state being independent of the level of vibrational excitation. However, for all the other outer valence ionic states, a disparity occurs between the observed and the simulated vibrational structure, and the measured β-parameters are at variance with the behavior expected at the level of the Franck–Condon approximation. Furthermore, these inconsistencies suggest that the excited electronic states may be interacting vibronically such that the nuclear dynamics occur over coupled potential energy surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

The Ratio of Ortho- to Para-H2 in Photodissociation Regions

We discuss the ratio of ortho- to para-H2 in photodissociation regions (PDRs). We draw attention to an apparent confusion in the literature between the ortho-to-para ratio of molecules in FUV-pumped vibrationally excited states and the total H2 ortho-to-para abundance ratio. These ratios are not the same because the process of FUV pumping of fluorescent H2 emission in PDRs occurs via optically thick absorption lines. Thus gas with an equilibrium ratio of ortho- to para-H2 equal to 3 will yield FUV-pumped vibrationally excited ortho-to-para ratios smaller than 3, because the ortho-H2 pumping rates are preferentially reduced by optical depth effects. Indeed, if the ortho and para pumping lines are on the "square root" part of the curve of growth, then the expected ratio of ortho and para vibrational line strengths is 3(sup 1/2) approximately 1.7, close to the typically observed value. Thus, contrary to what has sometimes been stated in the literature, most previous measurements of the ratio of ortho- to para-H2 in vibrationally excited states are entirely consistent with a total ortho-to-para ratio of 3, the equilibrium value for temperatures greater than 200 K. We present an analysis and several detailed models that illustrate the relationship between the total ratios of ortho- to para-H2 and the vibrationally excited ortho-to-para ratios in PDRs. Recent Infrared Space Observatory measurements of pure rotational and vibrational H2 emissions from the PDR in the star-forming region S140 provide strong observational support for our conclusions.

Sternberg, Amiel↗
NASA NTRS1994

Observations of the far ultraviolet airflow by the Ultraviolet Limb Imaging experiment on STS-39

The Ultraviolet Limb Imaging (UVLIM) experiment flew on STS-39 in the spring of 1991 to observe the Earth's thermospheric airglow and included a far ultraviolet (1080-1800 A) spectrometer. We present first results from this spectrometer, including a spectroscopic analysis at 6-A resolution of H, O, N, and N2 dayglow emissions and modeling of the observed limb-scan profiles of dayglow emissions. The observed N2 Lyman-Birge-Hopfield (LBH) emission reflects a vibrational population distribution in the a(1 Pi)(sub g) state that differs significantly from those predicted for direct electron excitation and excitation with cascade from the a('1 Sigma)(sub u)(-) and w(1 Delta)(sub u) states. The vibrational population distribution and LBH brightness suggest a total cascade rate 45% that of direct excitation, in contrast to laboratory measurements. For the first time, pronounced limb brightening is observed in both the N I lambda 1200 limb emission profiles, as expected for emissions excited by N2 dissociation which produces kinetically fast N fragments; however, optically thick components of these features are also observed. Preliminary modeling of the OI lambda 1356, HI lambda 1216, and OI lambda 1304 and OI lambda 1641 emissions agrees to within roughly 10% of the observed limb-scan profiles, but the models underestimate the N2 LBH profiles by a factor of 1.4-1.6, consistent with the inferred cascade effect. Other findings include: an OI lambda 1152/lambda 1356 intensity ratio that is inconsistent with the large cascade contribution to OI lambda 1356 from np 5P states required by laboratory and nightglow observations; nightglow observations of the tropical ultraviolet arcs exhibit a wide range of OI lambda 1356/lambda 1304 intensity ratios and illustrate the complicated observing geometry and radiative transfer effects that must be modeled; and we find a 3-sigma upper limit of 8.5 R to the total LBH vehicle glow emission.

Budzien, S. A.↗
NASA NTRS1971

Semiclassical vibration-rotation transition probabilities for motion in molecular state averaged potentials.

Collision-induced vibration-rotation transition probabilities are calculated from a semiclassical three-dimensional model, in which the collision trajectory is determined by the classical motion in the interaction potential that is averaged over the molecular rotational state, and compared with those for which the motion is governed by a spherically averaged potential. For molecules that are in highly excited rotational states, thus dominating the vibrational relaxation rate at high temperature, it is found that the transition probability for rotational state averaging is smaller than that for spherical averaging. For typical collisions, the transition cross section is decreased by a factor of about 1.5 to 2.

Stallcop, J. R.↗
NASA NTRS1995

Rotational And Rovibrational Energy Transfer In Electron Collisions With Molecules

Air flows around a hypervelocity reentry vehicle undergo dissociation, rovibrational excitation and ionization. More specifically the air, initially 80% N2 and 20% O2, in the shock layer consists of species such as N, O, N2, O2, NO, N+, O+, N+, O+, NO+ and 2 free electrons. It was pointed out in multi temperature models'' that the temperature of the rotational energy modes and the gas-kinetic translational temperature are quickly equilibrated by a few collisions and rise rapidly to high temperatures as 50000K before falling off to equilibrium value of 10000K. Contrary, the electronic and vibrational temperatures state energy distributions remain low (less than 15000K) because of the slow equilibration. Electron vibrational energy transfer is thought to play a crucial role in such a ionizing flow regime since chemical reaction rates and dissociation depend strongly on the vibrational temperatures. Modeling of these flowfields in principle require the rovibrational excitation and de-excitation cross section data for average electron energies from threshold up to several eV (leV=11605.4 K). In this lecture we focus on theoretical description of rotational effects i.e. energy transfer of electrons to molecules such that the molecular rotational (vojo goes to voj) or vibrational and rotational (v(sub 0)j(sub 0) goes to vj) states are changed. Excitation and de-excitation of electronic states was discussed in a previous talk at this conference.

Thuemmel, Helmar T.↗
NASA NTRS1995

Millimeter and Submillimeter Spectroscopy of Molecules of Atmospheric Importance

In our proposal we laid out work in three areas of relevance to atmospheric science: millimeter and submillimeter spectroscopy, variable temperature pressure broadening, and band and intensity measurements in the FIR. Below we will briefly discuss our progress during the second year of this project. In our millimeter and submillimeter (mm/submm) spectroscopic work, one of our goals has been to work towards the unification of the rotational (primarily obtained by mm/submm techniques) and rotational-vibrational (primarily obtained by infrared techniques) data sets in the context of theoretically well founded models which take advantage of the strengths of the data from each experimental technique. From the point of view of the development of the optimal data base for atmospheric observations, this is clearly a desirable goal. During the first year of this project we did an analysis of a weighted, mixed infrared and mm/submm data set of the n = 0, 1, and 2 torsional states of the ground vibrational state of HOOH. The purpose of this work is to provide a unified understanding of the spectrum, which is applicable in both the rotational and rotational - vibrational regimes. We have succeed in doing this in the context of a single weighted fit which accounts for both data sets to their respective experimental uncertainty (-0.1 and 10 MHz, respectively). Additionally, we have now done a similar analysis on the n = 0 torsional state of v(sub 3) and begun a similar analysis on v(sub 6). For several years we have been working on the mm/submm rotational spectra of the many excited vibrational states of HNO3, again with particular emphasis on the relationships between the mm/submm and infrared spectra. During the first year of this project we were able to use mm/submm spectroscopy to fully resolve the torsional splittings in 2 v(sub 9) and v(sub 5), establish a theoretically well founded quantitative relation between them, and show that both have their physical origin in the torsional motion of the v(sub 9) mode.This result has now been incorporated in a recent reanalysis of the infrared spectrum and has resulted in improved fits - eliminating what was in retrospect a systematic error associated with this previously unknown effect.

DeLucia, Frank C.↗
DOE OSTI2020

An ab initio exciton model for singlet fission

Here we present an ab initio exciton model that extends the Frenkel exciton model and includes valence, charge-transfer, and multiexcitonic excited states. It serves as a general, parameter-free, yet computationally efficient and scalable approach for simulation of singlet fission processes in multichromophoric systems. A comparison with multiconfigurational methods confirms that our exciton model predicts consistent energies and couplings for the pentacene dimer and captures the correct physics. Calculations of larger pentacene clusters demonstrate the computational scalability of the exciton model and suggest that the mixing between local and charge-transfer excitations narrows the gap between singlet and multiexcitonic states. Local vibrations of pentacene molecules are found to facilitate singlet–multiexcitonic state-crossing and hence are important for understanding singlet fission. The exciton model developed in this work also sets the stage for further implementation of the nuclear gradients and nonadiabatic couplings needed for first principles nonadiabatic quantum molecular dynamics simulations of singlet fission.

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

Inelastic, exchange, and reactive processes in rovibrationally excited collisions of HD with H

ABSTRACT The HD molecule is an important coolant in early universe chemistry models and a tracer of H2 in star-forming regions. Rate coefficients for collisional excitation and de-excitation of HD rotational and vibrational levels form important ingredients in astrophysical models. While collisions with He, H2, and H are the most important, available data for H + HD collisions are largely limited to temperatures less than 1000 K for the vibrational ground state, low-lying rotational levels of the v = 1 HD vibrational level, or computed without reactive contributions. Here, through explicit quantum scattering calculations, we report extensive data for rovibrational transitions in HD induced by H atoms for a range of rotational levels in v = 1 and some v = 0 levels for temperatures up to 1000 K. The significance of the computed results for astrophysical modeling is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Laser studies of the photodissociation dynamics of cometary radicals

In the past year, it was shown that in the 193 nm photolysis of C2H, the C2 radical is produced in a variety of electronic, vibrational, and rotational states. The relative population of the vibrational and rotational states of C2(A 1 Pi u), C2(B 1 Sigma g +), and C2(A 3 Pi u) were determined in a static gas cell and in a pulsed molecular beam. It seems as though the original angular momentum of the C2H molecule appears as part of the angular momentum of the C2 radical. A attempt is being made to discover the mathematical relationship that governs this mapping. New information about the bond dissociation energy of the C2 radical was produces. C2(b 3 Sigma g -) and C2( 1 Delta g) were detected in the photolysis of C2H via time resolved infrared emission spectroscopy. In the former case, vibrational excitation up to v'' = 4 is observed. All of the results suggest that the C2 models in comets need to consider the presence of vibrationally excited C2 radicals in comets. The laser induced fluorescence spectra of the C3 was observed as a product of the 193 nm photolysis of allene and propyne. The populations of the rotational levels are identical in both cases. This result has led us to conclude that an isomerization reaction occurs in the photolysis of propyne which leads to the same C3H2 intermediate that is formed in the photolysis of C3H4. Since the former molecule is one of the most abundant in the interstellar medium it is also likely that its precursor is also present in comets. This would explain why C3 is observed in comets.

Jackson, William M.↗
NASA NTRS1999

Diagnostics of Laser Produced Plume Under Carbon Nanotube Growth Conditions

This paper presents diagnostic data obtained from the plume of a graphite composite target during carbon nanotube production by the double-pulse laser oven method. The insitu emission spectrum (300 to 650 nm) is recorded at different locations upstream of the target and at different delay times from the lasers (IR and green). Spectral features are identified as emissions from C2 (Swan System: a (sup 3)pi(sub g) - delta (sup 3)pi(sub u) and C3 (Comet Head System: A (sup 1)pi(sub u) - chi (sup 1)sigma(sub u) (sup +). Experimental spectra are compared with computed spectra to estimate vibrational temperatures of excited state C2 in the range of 2500 to 4000 kappa The temporal evolution of the 510 nm band of C2 is monitored for two target positions in various locations which shows confinement of the plume in the inner tube and increase in plume velocity with temperature. The excitation spectra of C2 are obtained by using a dye laser to pump the (0,1) transition of the Swan System and collecting the Laser Induced Fluorescence signal from C2 These are used to obtain "ground-state" rotational and vibrational temperatures which are close to the oven temperature. Images of the plume are also collected and are compared with the spectral measurements.

Arepalli, Sivaram↗
DOE OSTI2023

Availability and reactivity of N 2 ( v ) for NH 3 synthesis by plasma catalysis

Production of vibrationally excited N 2 (N 2 (v)) in atmospheric pressure nonthermal plasma and loss of N 2 (v) by gas-phase reactions and reactions on catalytic surfaces are analyzed to examine the role of N 2 (v) in NH 3 formation by plasma catalysis. Vibrational state-to-state kinetic models complemented with molecular beam mass spectrometry (MBMS) measurements demonstrate that N 2 (v> 0) is produced with densities 100× greater than the density of N radicals by a radiofrequency atmospheric pressure plasma jet. The experimentally measured loss of N 2 (v) corresponds with a state-to-state kinetic model that describes loss of N 2 (v) by surface-mediated vibrational relaxation without consideration of reactions that convert N 2 (v) to NH 3 over the catalyst surface. Rate constants for vibrational relaxation of N 2 (v) on catalyst surfaces exceed upper bounds on proposed rate constants for NH 3 formation reactions from N 2 (v) over Fe when v < 9, Ni when v < 18, and Ag when v < 39, which indicates that only higher vibrational levels can possibly contribute to catalytic NH 3 formation faster than they undergo vibrational relaxation on the surface. Densities of N 2 (v> 8), vibrational levels that can possibly react over Fe to form NH 3 faster than they undergo vibrational relaxation, are less than or similar to N densities at the inlet of the catalyst bed and measured NH 3 formation for the investigated conditions in this work, while densities of N 2 (v> 17) and N 2 (v> 38) are orders of magnitude below the N density at the inlet of the catalyst bed and the measured NH 3 formation. The loss of N 2 (v) by vibrational relaxation on the surface limits the ability of N 2 (v) to contribute to catalytic NH 3 formation and explains why N 2 (v) does not produce NH 3 in quantities that are comparable to NH 3 formation from N even though N 2 (v > 0) is more abundantly produced by the plasma.

state-to-state kinetic modeling↗
NASA NTRS1972

Photodissociation of CS2 in the vacuum ultraviolet - Determination of bond dissociation energy from the lowest vibrational level of the ground state CS2.

Photolysis in the vacuum ultraviolet results almost exclusively in the production of S(super-3)P atoms, which is in apparent violation of spin conservation. The threshold energy of incident photons required to produce fluorescence was used to calculate the bond dissociation energy (from the lowest vibrational level of the ground state), and the result agrees with the value previously derived from the photoionization of CS2. The fluorescence excitation spectrum shows peaks corresponding to Rydberg series I and II, indicating that the observed photodissociation of CS2 in the vacuum ultraviolet is mainly the result of predissociation from Rydberg states. The absorption coefficient of CS2 was measured in the region of 1200 to 1400 A.

Okabe, H.↗