Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “atomic and molecular collisions”

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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Angular Distribution of Characteristic Radiation Following the Excitation of He-Like Uranium in Relativistic Collisions

In this paper, we present an experimental and theoretical study of excitation processes for the heaviest stable helium-like ion, that is, He-like uranium occurring in relativistic collisions with hydrogen and argon targets. In particular, we concentrate on angular distributions of the characteristic Kα radiation following the K → L excitation of He-like uranium. We pay special attention to the magnetic sub-level population of the excited 1s2lj states, which is directly related to the angular distribution of the characteristic Kα radiation. We show that the experimental data can be well described by calculations taking into account the excitation by the target nucleus as well as by the target electrons. Moreover, we demonstrate for the first time an important influence of the electron-impact excitation process on the angular distributions of the Kα radiation produced by excitation of He-like uranium in collisions with different targets.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Angular correlation between the fission fragment intrinsic spins

The generation of fission fragment (FF) spins and of their relative orbital angular momentum has been debated for more than six decades, and no consensus has been achieved so far. The interpretation of recent experimental results of Wilson et al., has been challenged by several recent theoretical studies, which are not in agreement with one another. According to the interpretation by Wilson et al., the FF spins emerge very long after scission occurrs. Randrup and Vogt, while agreeing that the FF spins are uncorrelated, conclude on the basis of a phenomenological model that these spins are uncorrelated already before scission. Bulgac et al., in a fully microscopic study demonstrate that the primordial FF spin final values are defined before the emission of prompt neutrons and statistical gammas and are strongly correlated with a relative angle between spins close to 2π/3, a result in full agreement with the present independent analysis. The prompt neutrons and statistical gammas carry a significant amount of angular momentum according to the study of Stetcu et al. which can lead to a decorrelation of the FF bandhead spins of the yrast lines measured by Wilson et al., and which also provides arguments why these measured spins are so different from the primordial FF spins evaluated by Bulgac et al.. Here, I show that the unexpected character of the angular correlation between the primordial FF intrinsic spins, recently evaluated by Bulgac et al., which favors FF intrinsic spins pointing predominantly in opposite directions, can be understood by using simple general phase space arguments. The observation by Wilson et al., that the FF spins are uncorrelated follows from both the results of the microscopic calculation of Bulgac et al., and the present analysis of the full correlated probability distribution of the FF spins together with the relative orbital angular momentum of the primordial FFs. These arguments may apply also to heavy-ion collisions and, since there is no use of specifics of the particle interactions, the present results might apply to atomic and molecular systems as well.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Adiabatic and post-adiabatic hyperspherical treatment of the huge ungerade proton-hydrogen scattering length

While the hydrogen molecular ion is the simplest molecule in nature and very well studied in all of its properties, it remains an interesting system to use for explorations of fundamental questions. One such question treated in this study relates to finding an optimal adiabatic representation of the physics, i.e., the best adiabatic description that minimizes the role of nonadiabatic effects. As a test case explored here in detail, we consider the ungerade symmetry of $H$$^{+}_{2}$, which is known to have a huge scattering length of order 750 Bohr radii, and an incredibly weakly bound excited state. We show that a hyperspherical adiabatic description does an excellent job of capturing the main physics. Furthermore, our calculation yields a competitive scattering length and shows that nonadiabatic corrections are small and can even be adequately captured using the post-adiabatic theory of Klar and Fano.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1984

Atomic hydrogen maser measurements with wall surfaces of carbon tetrafluoride

The principal objectives of the Smithsonian Astrophysical Observatory cold maser research programs are given. This work is aimed principally at understanding more about the interaction of hydrogen atoms with wall coatings of fluorinated ethylene propylene (Dupont Teflon FEP-120 co-polymer) and of carbon tetrafluoride (CE4). The principal measured quantity in these experiments is the wall shift of the maser's output frequency. The wall shift per atomic collision was calculated from the measured wall frequency shift. This assumes that the wall surface area is smooth on a molecular scale.

Vessot, R. F. C.↗
DOE OSTI2026

Vibrationally resolved cross sections for proton collisions with hydrogen molecules

The semi-classical molecular convergent close-coupling approach has been applied to proton collisions with molecular hydrogen in the ground electronic and vibrational state. Cross sections for electron loss and electron capture agree well with the experimental data in the intermediate energy range where coupling between electronic reaction channels is strong and previously available calculations produce inconsistent results. Results for elastic scattering and total excitation are compared with effective one-electron coupled-channel calculations, showing that accurate target structure makes an important difference to these cross sections at intermediate energies. The excitation cross sections are calculated using both the fixed-nuclei and adiabatic-nuclei approximations for transitions from the $X^1Σ^+_{\textrm{g}}$ state to the $B^1Σ^+_{\textrm{u}}$, $B'$$^1Σ^+_{\textrm{u}}$, $B''$$^1Σ^+_{\textrm{u}}$, $EF$$^1Σ^+_{\textrm{g}}$, $GK$$^1Σ^+_{\textrm{g}}$, $H$$^1Σ^+_{\textrm{g}}$, $C$$^1Π_{\textrm{u}}$, $D$$^1Π_{\textrm{u}}$, $D'$$^1Π_{\textrm{u}}$, $I$$^1Π_{\textrm{u}}$, and $J$$^1Δ_{\textrm{g}}$ states for proton energies from to keV. We find significant differences between the present ab initio calculations and the equivelocity scaled electron-scattering data that is currently used for collisional-radiative modelling. Furthermore, the adiabatic-nuclei calculations enable us to resolve the final vibrational level after excitation, producing a complete set of cross sections for excitation of ground-state molecular hydrogen for all electronic states up to $n = 3$, where $n$ is the united-atoms-limit principle quantum number.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Directed Gas-Phase Formation of The Propargyl Family of Resonance-Stabilized Radicals in The Reactions of Ground-State Carbon Atoms (C; 3 P j ) with Butene Isomers (C 4 H 8 ): Dimethylpropargyl and Ethylpropargyl

The propargyl radical (C 3 H 3 ) is the simplest resonance-stabilized free radical (RSFR), but how does stepwise methyl substitution in the alkene reactant affect its dynamics of their formation? We report a crossed molecular beam study of the reactions of atomic carbon (C, 3 P j ) with four butene isomers (C 4 H 8 ) under single collision conditions at a collision energy of 28 ± 2 kJ mol −1 . Barrierless addition of atomic carbon to the alkene C=C bond triggers ring opening to triplet substituted allenes—a de facto insertion mechanism—followed by unimolecular decomposition via atomic hydrogen (H), methyl (CH 3 ) or ethyl (C 2 H 5 ) loss, yielding a family of propargyl‑type RSFRs. RRKM calculations reveal that the branching ratios are highly sensitive to the alkene structure. While the methyl loss channel, affording 1‑methylpropargyl, dominates for 2 butenes (80–90%), the predicted hydrogen atom loss channel (≈10%) leading to 1,3 dimethylpropargyl is identified in the experiment by comparison with theoretical energetics. For isobutene, a near‑equal competition is seen, with the reaction producing 3‑methylpropargyl (≈50%) and 1,1‑dimethylpropargyl (≈40%), along with 2‑vinylallyl (≈5%), whose formation is supported by the experimental data. Most notably, the reaction with 1 butene uniquely favors an enthalpically driven hydrogen shift, eventually producing 1 vinylallyl (≈38%), which is assigned based on the excellent agreement between the measured and calculated reaction exothermicity. Rapid entropically favored fragmentation channels yield ≈40% of propargyl type species (propargyl, 1- and 3-ethylpropargyls), slightly outcompeting the allyl type product. Furthermore, these results establish a systematic progression from C 2 H 4 to C 4 H 8 , where the increasing alkyl substitution unlocks new fragmentation channels, providing a versatile gas phase route to alkylated RSFRs—key intermediates in the growth of methylated and ethylated PAHs and aliphatic chains in combustion and cold interstellar environments (molecular clouds).

Alkyls↗
DOE OSTI2025

Gas-phase synthesis of naphthalene through an unconventional thermal alkyne–alkene [2 + 2] cycloaddition mechanism

Exotic cycloaddition entrance channels were discovered for the bimolecular gas-phase reactions of the phenylethynyl radical (C 6 H 5 CC, X 2 A 1 ) with ethylene-d 4 (C 2 D 4 ) and propylene (C 3 H 6 ) as explored under single-collision conditions utilizing the crossed molecular beams technique combined with electronic structure and statistical calculations. Connecting the concepts of barrierless entrance channels, excited states, and facile non-photochemically activated cycloadditions, the reaction pathway features an unconventional thermal [2 + 2] cycloaddition forming a four-membered ring collision complex followed by multiple isomerizations prior to unimolecular decomposition via atomic hydrogen loss to (un)substituted naphthalenes—naphthalene-d 4 (C 10 H 4 D 4 ) and 1-/2-methylnaphthalene (C 11 H 10 ). The small energy gap between the singly-occupied a 1 highest occupied molecular orbital (HOMO) with a σ-character and the underlying doubly-occupied b 1 molecular orbital with a π-character allows a facile promotion of an electron. This in turn enables a versatile low-temperature reactivity of phenylethynyl, where the end-on and side-on barrierless approaches of ethylene are due to its interaction with the σ and π orbitals, respectively, thus suggesting this mechanism as a possible method for tuning substituents in polycyclic aromatic hydrocarbon (PAH) formation and highlighting its versatility as a probe of fundamental carbon chemistry via counterintuitive cycloaddition reactions under single-collision conditions.

Goettl, Shane J. [University of Hawaii at Manoa, H↗
DOE OSTI2026

Non-adiabatic quantum interference and complex formation in ultracold collisions of Rb with KRb

Ultracold elastic collisions of 87 Rb with 40 K 87 Rb in its ground vibrational and rotational state are investigated using a first principles based theoretical methodology. Full-dimensional ab initio computed potential energy surfaces are reported that include the two lowest-lying electronic states, their conical intersection, non-adiabatic couplings and an accurate long-range behavior. A numerically exact time-independent quantum dynamics method in hyperspherical coordinates is used to compute the elastic scattering cross sections, rate coefficients and collision lifetime spectrum. The quantum scattering calculations include all degrees of freedom and treat both electronic states and their non-adiabatic couplings using a two-state diabatic representation. The theoretically computed elastic rate coefficient is in good agreement with the recently reported experimental value. Significant non-adiabatic quantum interference effects are shown to originate from the unique properties of ultracold collisions and the geometric phase associated with the conical intersection. A high-resolution collision energy grid is used to investigate the origin of the experimentally reported long-lived 3-body collision complexes.

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

Ab initio quantum scattering calculations and a new potential energy surface for the HCl( X 1Σ+)–O2(X3Σg−) system: Collision-induced line shape parameters for O2-perturbed R(0) 0–0 line in H35Cl

The remote sensing of abundance and properties of HCl—the main atmospheric reservoir of Cl atoms that directly participate in ozone depletion—is important for monitoring the partitioning of chlorine between “ozone-depleting” and “reservoir” species. Such remote studies require knowledge of the shapes of molecular resonances of HCl, which are perturbed by collisions with the molecules of the surrounding air. In this work, we report the first fully quantum calculations of collisional perturbations of the shape of a pure rotational line in H35Cl perturbed by an air-relevant molecule [as the first model system we choose the R(0) line in HCl perturbed by O2]. The calculations are performed on our new highly accurate HCl(X1Σ+)–O2(X3Σg−) potential energy surface. In addition to pressure broadening and shift, we also determine their speed dependencies and the complex Dicke parameter. This gives important input to the community discussion on the physical meaning of the complex Dicke parameter and its relevance for atmospheric spectra (previously, the complex Dicke parameter for such systems was mainly determined from phenomenological fits to experimental spectra and the physical meaning of its value in that context is questionable). We also calculate the temperature dependence of the line shape parameters and obtain agreement with the available experimental data. We estimate the total combined uncertainties of our calculations at 2% relative root-mean-square error in the simulated line shape at 296 K. This result constitutes an important step toward computational population of spectroscopic databases with accurate ab initio line shape parameters for molecular systems of terrestrial atmospheric importance.

Chemistry↗
DOE OSTI2024

Elucidating the chemical dynamics of the elementary reactions of the 1-propynyl radical (CH 3 CC; X 2 A 1 ) with 2-methylpropene ((CH 3 ) 2 CCH 2 ; X 1 A 1 )

Exploiting the crossed molecular beam technique, we studied the reaction of the 1-propynyl radical (CH 3 CC; X 2 A 1 ) with 2-methylpropene (isobutylene; (CH 3 ) 2 CCH 2 ; X 1 A 1 ) at a collision energy of 38 ± 3 kJ mol –1 . The experimental results along with ab initio and statistical calculations revealed that the reaction has no entrance barrier and proceeds via indirect scattering dynamics involving C 7 H 11 intermediates with lifetimes longer than their rotation period(s). The reaction is initiated by the addition of the 1-propynyl radical with its radical center to the π-electron density at the C1 and/or C2 position in 2-methylpropene. Further, the C 7 H 11 intermediate formed from the C1 addition either emits atomic hydrogen or undergoes isomerization via [1,2-H] shift from the CH 3 or CH 2 group prior to atomic hydrogen loss preferentially leading to 1,2,4-trimethylvinylacetylene (2-methylhex-2-en-4-yne) as the dominant product. The molecular structures of the collisional complexes promote hydrogen atom loss channels. RRKM results show that hydrogen elimination channels dominate in this reaction, with a branching ratio exceeding 70%. Since the reaction of the 1-propynyl radical with 2-methylpropene has no entrance barrier, is exoergic, and all transition states involved are located below the energy of the separated reactants, bimolecular collisions are feasible to form trimethylsubstituted 1,3-enyne (p1) via a single collision event even at temperatures as low as 10 K prevailing in cold molecular clouds such as G+0.693. As a result, the formation of trimethylsubstituted vinylacetylene could serve as the starting point of fundamental molecular mass growth processes leading to di- and trimethylsubstituted naphthalenes via the HAVA mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Viscosity of dissociating gases

Recent calculations of the viscosity of iodine suggest that existing predictions of viscosities of high-temperature (up to several thousands degrees) gases should be revised, with much more attention being paid to the atomic and molecular interactions in the gas. As the gas starts to dissociate, the frequency of atom-molecule and atom-atom interactions increases, and those collisions must be taken into account in calculations of viscosity at high temperature. In this study, the iodine is chosen as an example, and the dependence of its viscosity on the gas dissociation degree is shown. Several possible channels for I+I interaction are considered in addition to I+I2 and I2+I2 collisions, and the resulting collision integrals are averaged over all the important channels.

Kang, S. H.↗
NASA NTRS1972

Excitation of sodium D-line radiation in collisions of sodium atoms with internally excited H2, D2 and N2.

Excitation of D-line radiation in collisions of Na atoms with vibrationally excited N2, H2, and D2 was studied in two modulated crossed-beam experiments. In both experiments, the molecular excitation was provided by heating the molecular beam to temperatures which were assumed to give populations corresponding to the Boltzmann distribution. In the first experiment, a total rate coefficient was measured as a function of molecular beam temperature. The second experiment achieved partial separation of internal vs kinetic energy transfer effects by using a velocity-selected molecular beam. The data from both experiments were used to determine parameters for the dependence of the transfer cross section upon the kinetic energy for a given change in the vibrational quantum number. Results indicate that most of the Na excitation energy comes from internal vibrational energy, with the remainder coming from kinetic energy.

Krause, H. F.↗
NASA NTRS1990

Novel laser gain and time-resolved FTIR studies of photochemistry

Several techniques are discussed which can be used to explore laboratory photochemical processes and kinetics relevant to planetary atmospheres; these include time-resolved laser gain-versus-absorption spectroscopy and time-resolved Fourier transform infrared (FTIR) emission studies. The laser gain-versus-absorption method employed tunable diode and F-center lasers to determine the yields of excited photofragments and their kinetics. The time-resolved FTIR technique synchronizes the sweep of a commercial FTIR with a pulsed source of light to obtain emission spectra of novel transient species in the infrared. These methods are presently being employed to investigate molecular photodissociation, the yields of excited states of fragments, their subsequent reaction kinetics, Doppler velocity distributions, and velocity-changing collisions of translationally fast atoms. Such techniques may be employed in future investigations of planetary atmospheres, for example to study polycyclic aromatic hydrocarbons related to cometary emissions, to analyze acetylene decomposition products and reactions, and to determine spectral features in the near infrared and infrared wavelength regions for planetary molecules and clusters.

Leone, Stephen R.↗
NASA NTRS1976

Interactions of satellite-speed helium atoms with satellite surfaces. 2: Energy distributions of reflected helium atoms

Energy transfer in collisions of satellite-speed (7,000 m/sec) helium atoms with a cleaned 6061-T6 satellite-type aluminum surface was investigated using the molecular-beam technique. The amount of energy transferred was determined from the measured energy of the molecular-beam and the measured spatial and energy distributions of the reflected atoms. Spatial distributions of helium atoms scattered from a 6061-T6 aluminum surface were measured. The scattering pattern exhibits a prominent backscattering, probably due to the gross surface roughness and/or the relative lattice softness of the aluminum surface. Energy distributions of reflected helium atoms from the same surface were measured for six different incidence angles. For each incidence angle, distributions were measured at approximately sixty scattering positions. At a given scattering position, the energy spectra of the reflected helium atoms and the background gas were obtained using the retarding-field energy analyzer.

Liu, S. M.↗
NASA NTRS1984

Infrared spectroscopy of interstellar shocks

Infrared emission lines from interstellar shocks provide valuable diagnostics for violent events in the interstellar medium, such as supernova remnants and mass outflow from young stellar objects. There are two types of interstellar shocks: in J shocks, gas properties 'jump' from their preshock to their postshock values in a shock front with a thickness equal to or less than one mean free path; radiation is emitted behind the shock front, primarily in the visible and ultraviolet, but with a few strong infrared lines, such as OI(63 microns). Such shocks occur in ionized or neutral atomic gas, or at high velocities (equal to or greater than 50 km/s) in molecular gas. In C shocks, gas is accelerated and heated by collisions between charged particles, which have a low concentration and are coupled to the magnetic field, and neutral particles; radiation is generated throughout the shock and is emitted almost entirely in infrared emission lines. Such shocks occur in weakly ionized molecular gas for shock velocities below about 50 km/s.

Mckee, C. F.↗
NASA NTRS1995

Molecular vibrational states during a collision

Alternative algebraic techniques to approximate a given Hamiltonian by a harmonic oscillator are described both for time-independent and time-dependent systems. We apply them to the description of a one dimensional atom-diatom collision. From the resulting evolution operator, we evaluate vibrational transition probabilities as well as other time-dependent properties. As expected, the ground vibrational state becomes a squeezed state during the collision.

Recamier, Jose A.↗
NASA NTRS1978

Transport properties in the atmosphere of Jupiter

The calculation of transport properties near the surface of a probe entering the atmosphere of Jupiter is discussed for (1) transport properties in the pure Jovian atmosphere, (2) transport properties for collisions between monatomic carbon atoms, including the effect of excited electronic states, (3) transport properties at the boundaries for mixing of the pure Jovian atmosphere and the atmosphere due to the injection of gaseous ablation products, and (4) transport properties for interactions involving some of the molecular ablation products. The transport properties were calculated using the kinetic theory of gases. Transport collision integrals were calculated for only a limited set of empirical and semiempirical interaction potentials. Since the accuracy of the fit of these empirical potentials to the true potential usually determines the accuracy of the calculation of the transport properties, the various interaction potentials used in these calculations are discussed.

Biolsi, L., Jr.↗