SEARCH · Search NASA
Results for “PES”
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.
From photoelectron detachment spectra of BrHBr{sup −}, BrDBr{sup −} and IHI{sup −}, IDI{sup −} to vibrational bonding of BrMuBr and IMuI
Photoelectron detachment XLX{sup −}(00{sup 0}0) + hν → XLX(vib) + e{sup −} + KER (X = Br or I, L = H or D) at sufficiently low temperatures photoionizes linear dihalogen anions XLX{sup −} in the vibrational ground state (v{sub 1}v{sub 2}{sup l}v{sub 3} = 00{sup 0}0) and prepares the neutral radicals XLX(vib) in vibrational states (vib). At the same time, part of the photon energy (hν) is converted into kinetic energy release (KER) of the electron [R. B. Metz, S. E. Bradforth, and D. M. Neumark, Adv. Chem. Phys. 81, 1 (1992)]. The process may be described approximately in terms of a Franck-Condon type transfer of the vibrational wavefunction representing XLX{sup −}(00{sup 0}0) from the domain close to the minimum of its potential energy surface (PES) to the domain close to the linear transition state of the PES of the neutral XLX. As a consequence, prominent peaks of the photoelectron detachment spectra (pds) correlate with the vibrational energies E{sub XLX,vib} of states XLX(vib) which are centered at linear transition state. The corresponding vibrational quantum numbers may be labeled vib = (v{sub 1}v{sub 2}{sup l}v{sub 3}) = (00{sup 0}v{sub 3}). Accordingly, the related most prominent peaks in the pds are labeled v{sub 3}. We construct a model PES which mimics the “true” PES in the domain of transition state such that it supports vibrational states with energies E{sub XLX,pds,00{sup 0}v{sub 3}} close to the peaks of the pds labeled v{sub 3} = 0, 2, and 4. Subsequently, the same model PES is also used to calculate approximate values of the energies E{sub XMuX,00{sup 0}0} of the isotopomers XMuX(00{sup 0}0). For the heavy isotopomers XHX and XDX, it turns out that all energies E{sub XLX,00{sup 0}v{sub 3}} are above the threshold for dissociation, which means that all heavy XLX(00{sup 0}v{sub 3}) with wavefunctions centered at the transition state are unstable resonances with finite lifetimes. Turning the table, bound states of the heavy XLX are van der Waals (vdW) bonded. In contrast, the energies E{sub XMuX,00{sup 0}0} of the light isotopomers XMuX(00{sup 0}0) are below the threshold for dissociation, with wavefunctions centered at the transition state. This means that XMuX(00{sup 0}0) are vibrationally bonded. This implies a fundamental change of the nature of chemical bonding, from vdW bonding of the heavy XHX, XDX to vibrational bonding of XMuX. For BrMuBr, the present results derived from experimental pds of BrHBr{sup −} and BrDBr{sup −} confirm the recent discovery of vibrational bonding based on quantum chemical ab initio calculations [D. G. Fleming, J. Manz, K. Sato, and T. Takayanagi, Angew. Chem., Int. Ed. 53, 13706 (2014)]. The extension from BrLBr to ILI means the discovery of a new example of vibrational bonding. These empirical results for the vibrational bonding of IMuI, derived from the photoelectron spectra of IHI{sup −} and IDI{sup −}, are supported by ab initio simulations of the spectra and of the wavefunction representing vibrational bonding of IMuI.
Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex
Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO{sub 2}–N{sub 2} van der Waals complex is generated using the explicitly correlated coupled cluster with single, double, and perturbative triple excitation (CCSD(T)-F12) method in conjunction with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. This 4D-PES is mapped along the intermonomer coordinates. An analytic fit of this 4D-PES is performed. Our extensive computations confirm that the most stable form corresponds to a T-shape structure where the nitrogen molecule points towards the carbon atom of CO{sub 2}. In addition, we located a second isomer and two transition states in the ground state PES of CO{sub 2}–N{sub 2}. All of them lay below the CO{sub 2} + N{sub 2} dissociation limit. This 4D-PES is flat and strongly anisotropic along the intermonomer coordinates. This results in the possibility of the occurrence of large amplitude motions within the complex, such as the inversion of N{sub 2}, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C{sub 2v} structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.
Kinetic isotope effect of the {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study
The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2} reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.
Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions
Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.
Predicting interface structure using the minima hopping method
Here, we adapt the minima hopping method (MHM) to the problem of interfacial structure prediction and apply it to study a canonical problem, the tilt grain boundaries in SrTiO 3 . Our method employs a hybrid approach by first exploring the potential energy surface (PES) of different grain boundary samplings with an empirical force field, among which the fifteen candidates with lower energies are then refined using ab initio density functional theory (DFT) calculations. During the exploratory stage, we bias the search using a local order parameter to primarily sample various reconstructions in the vicinity of the interface, while preserving the crystallinity of the bulk regions. We further enhance the search by incorporating initial structures with rigid body displacements to account for translational variations between bulk phases, enabling the MHM to effectively generate both stoichiometric and nonstoichiometric SrTiO 3 Σ3(111)[110] and Σ3(112)[110] grain boundaries. From an algorithmic standpoint, MHM outperforms earlier studies based on genetic algorithms (GA) by identifying more stable interfacial structures of several SrTiO 3 grain boundaries. The performance of the present implementation of the MHM approach is primarily limited by exploring an approximate description of the PES with a rather simple Buckingham potential. This limitation leads to variations in performance when compared to approaches utilizing more advanced surrogate PES models, such as direct DFT-PES sampling or GA with the embedded atom method (EAM). Despite the present limitations, the MHM approach is able to yield interfacial structures with comparable or lower interfacial energies in specific cases, such as Σ3(111)[110] Γ=1, ±0.5 and Σ3(112)[110] Γ= ±1, −2, underscoring the robustness of the MHM approach even with a simple approximation of the DFT PES. The MHM interfacial structure prediction method thus offers an efficient approach to understanding the grain boundaries and heterointerfaces at the atomic scale, providing an important prerequisite for effective materials design.
Crystallization histories of the group IIF iron meteorites and Eagle Station pallasites
The group IIF iron meteorites and Eagle Station pallasites (PES) have highly siderophile element abundances (HSE; Re, Os, Ir, Ru, Pt, and Pd) of metal that are consistent with formation in planetesimal cores by fractional crystallization with minor to major solid metal-liquid metal mixing. Modeling of HSE abundances of the IIF irons indicates a complex formation history that included the mixing of primitive and evolved solid and liquid metals. By contrast, modeling of HSE abundances of PES metal suggests these meteorites formed mainly as equilibrium solids from a common liquid. Abundances of some of the siderophile elements in the IIF irons and PES are permissive of a common core origin, however, the abundances of W and Ni indicate the PES ultimately formed on a more oxidized body. The PES most likely formed by the injection of olivine present at the core-mantle boundary into a metallic core liquid as a result of impact. The core then crystallized inward, trapping the olivine.
SU-E-T-405: Robustness of Volumetric-Modulated Arc Therapy (VMAT) Plans to Systematic MLC Positional Errors
Purpose: To evaluate the dosimetric impact of systematic MLC positional errors (PEs) on the quality of volumetric-modulated arc therapy (VMAT) plans. Methods: Five patients with head-and-neck cancer (HN) and five patients with prostate cancer were randomly chosen for this study. The clinically approved VMAT plans were designed with 2–4 coplanar arc beams with none-zero collimator angles in the Pinnacle planning system. The systematic MLC PEs of 0.5, 1.0, and 2.0 mm on both MLC banks were introduced into the original VMAT plans using an in-house program, and recalculated with the same planned Monitor Units in the Pinnacle system. For each patient, the original VMAT plans and plans with MLC PEs were evaluated according to the dose-volume histogram information and Gamma index analysis. Results: For one primary target, the ratio of V100 in the plans with 0.5, 1.0, and 2.0 mm MLC PEs to those in the clinical plans was 98.8 ± 2.2%, 97.9 ± 2.1%, 90.1 ± 9.0% for HN cases and 99.5 ± 3.2%, 98.9 ± 1.0%, 97.0 ± 2.5% for prostate cases. For all OARs, the relative difference of Dmean in all plans was less than 1.5%. With 2mm/2% criteria for Gamma analysis, the passing rates were 99.0 ± 1.5% for HN cases and 99.7 ± 0.3% for prostate cases between the planar doses from the original plans and the plans with 1.0 mm MLC errors. The corresponding Gamma passing rates dropped to 88.9 ± 5.3% for HN cases and 83.4 ± 3.2% for prostate cases when comparing planar doses from the original plans and the plans with 2.0 mm MLC errors. Conclusion: For VMAT plans, systematic MLC PEs up to 1.0 mm did not affect the plan quality in term of target coverage, OAR sparing, and Gamma analysis with 2mm/2% criteria.
Experimental evaluation of wall Mach number distributions of the octagonal test section proposed for NASA Lewis Research Center's altitude wind tunnel
Wall Mach number distributions were determined over a range of test-section free-stream Mach numbers from 0.2 to 0.92. The test section was slotted and had a nominal porosity of 11 percent. Reentry flaps located at the test-section exit were varied from 0 (fully closed) to 9 (fully open) degrees. Flow was bled through the test-section slots by means of a plenum evacuation system (PES) and varied from 0 to 3 percent of tunnel flow. Variations in reentry flap angle or PES flow rate had little or no effect on the Mach number distributions in the first 70 percent of the test section. However, in the aft region of the test section, flap angle and PES flow rate had a major impact on the Mach number distributions. Optimum PES flow rates were nominally 2 to 2.5 percent wtih the flaps fully closed and less than 1 percent when the flaps were fully open. The standard deviation of the test-section wall Mach numbers at the optimum PES flow rates was 0.003 or less.
Experimental evaluation of blockage ratio and plenum evacuation system flow effects on pressure distribution for bodies of revolution in 0.1 scale model test section of NASA Lewis Research Center's proposed altitude wind tunnel
An experimental investigation was conducted in the slotted test section of the 0.1-scale model of the proposed Altitude Wind Tunnel to evaluate wall interference effects at tunnel Mach numbers from 0.70 to 0.95 on bodies of revolution with blockage rates of 0.43, 3, 6, and 12 percent. The amount of flow that had to be removed from the plenum chamber (which surrounded the slotted test section) by the plenum evacuation system (PES) to eliminate wall interference effects was determined. The effectiveness of tunnel reentry flaps in removing flow from the plenum chamber was examined. The 0.43-percent blockage model was the only one free of wall interference effects with no PES flow. Surface pressures on the forward part of the other models were greater than interference-free results and were not influenced by PES flow. Interference-free results were achieved on the aft part of the 3- and 6-percent blockage models with the proper amount of PES flow. The required PES flow was substantially reduced by opening the reentry flaps.
Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface
The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.
The Galileo Probe: How it Has Changed Our Understanding of Jupiter
The Galileo Mission to Jupiter, which arrived in December of 1995, provided the first study by an orbiter, and the first in-situ sampling via an entry probe, of an outer planet atmosphere. The rationale for an entry probe is that, even from an orbiter, remote sensing of the jovian atmosphere could not adequately retrieve the information desired. This paper provides a current summary of the most significant aspects of the data returned from the Galileo entry probe. As a result of the probe measurements, there has been a reassessment of our understanding of outer planet formation and evolution of the solar system. The primary scientific objective of the Galileo probe was to determine the composition of the jovian atmosphere, which from remote sensing remained either very uncertain, or completely unknown, with respect to several key elements. The probe found that the global He mass fraction is. significantly above the value reported from the Voyager Jupiter flybys but is slightly below the protosolar value, implying that there has been some settling of He to the deep jovian interior. The probe He measurements have also led to a reevaluation of the Voyager He mass fraction for Saturn, which is now determined to be much closer to that of Jupiter. The elements C, N, S, Ar, Kr, Xe were all found to have global abundances approximately 3 times their respective solar abundances. This result has raised a number of fundamental issues with regard to properties of planetesimals and the solar nebula at the time of giant planet formation. Ne, on the other hand, was found to be highly depleted, probably as the result of it being carried along with helium as helium settles towards the deep interior. The global abundance of O was not obtained by the probe because of the influence of local processes at the probe entry site (PES), processes which depleted condensible species, in this case H2O, well below condensation levels. Other condensible species, namely NH3 and H2S, were similarly affected but attained their deep equilibrium mixing ratios before the maximum depth sampled by the probe. Processes that might be capable of producing such effects on the condensibles are still under investigation. Measured isotopic ratios of noble gases and other heavy elements are solar, and (D + (Sup 3)He)/H is the same to within measurement uncertainties as in the local interstellar medium. No thick clouds were detected, and in particular no significant water cloud, but the PES location clearly affected the probe measurements of clouds. In fact, the probe data must be understood in the context of the location of the PES, which was within what is termed a 5 micron hot spot, a local clearing in the clouds that is bright near the 5 microns spectral region. The thermal structure at the PES was determined from approximately 1000 km above the 1 bar pressure level (10(exp -9 bars)) to 132 km 1 bar (22bars). The probe showed the atmosphere to have a generally sub-adiabatic temperature gradient (static stability) of = 0.1 K/km to as deep as the probe made measurements. In the upper atmosphere the probe derived a maximum positive vertical temperature gradient of approximately 5 K/km, and maximum temperature of = 900 K. The energy sources producing the warm upper atmosphere have yet to be completely identified. At first glance, Doppler tracking of the probe indicates that the long observed cloud level zonal winds extend to levels at least as deep as the probe made measurements. Zonal wind increases from = 80 m/s at pressures less than a bar to about 180 m/s near 5 bars, and remains approximately constant with depth thereafter. However, there is a question as to whether the winds measured from probe tracking are representative of the general wind field, or are considerably influenced by localized winds associated with the PES.
Vibrational energy levels for CH4 from an ab initio potential
Many areas of astronomy and astrophysics require an accurate high temperature spectrum of methane (CH4). The goal of the present research is to determine an accurate ab initio potential energy surface (PES) for CH4. As a first step towards this goal, we have determined a PES including up to octic terms. We compare our results with experiment and to a PES based on a quartic expansion. Our octic PES gives good agreement with experiment for all levels, while the quartic PES only for the lower levels.
Electronic Structure, Localization and 5f Occupancy in Pu Materials
The electronic structure of delta plutonium ({delta}-Pu) and plutonium compounds is investigated using photoelectron spectroscopy (PES). Results for {delta}-Pu show a small component of the valence electronic structure which might reasonably be associated with a 5f{sup 6} configuration. PES results for PuTe are used as an indication for the 5f{sup 6} configuration due to the presence of atomic multiplet structure. Temperature dependent PES data on {delta}-Pu indicate a narrow peak centered 20 meV below the Fermi energy and 100 meV wide. The first PES data for PuCoIn5 indicate a 5f electronic structure more localized than the 5fs in the closely related PuCoGa{sub 5}. There is support from the PES data for a description of Pu materials with an electronic configuration of 5f{sup 5} with some admixture of 5f{sup 6} as well as a localized/delocalized 5f{sup 5} description.
Sequential Infiltration Synthesis of Al 2 O 3 in Polyethersulfone Membranes
We report the sequential infiltration synthesis (SIS) of aluminum oxide (Al 2 O 3 ) into polyethersulfone (PES) ultrafiltration (UF) membranes to form hybrid nanocomposites. SIS relies on chemical interactions between precursor vapors and polymer functional groups, and enables nucleation and growth of inorganic materials to controlled depth. Using in situ Fourier-transform infrared spectroscopy and ellipsometry measurements, we demonstrate that trimethylaluminum associates with the sulfonyl groups in PES, extending the library of SIS-modified polymer nanocomposites to a previously undescribed polymer system and new application space: PES UF membranes. Depth-profiled x-ray photoelectron spectroscopy showed that the trimethylaluminum purge time dictates the extent of Al 2 O 3 infiltration. Energy dispersive spectroscopy revealed the differences between SIS and atomic layer deposition in the membranes. Furthermore, this work demonstrates the viability of SIS to access the entire macroporous volume of PES UF membranes.
Atmospheric pressure plasma - $\mathrm{ARGET}$ $\mathrm{ATRP}$ modification of poly(ether sulfone) membranes: A combination attack
We report a novel surface modification technique for grafting alkyl methacrylate monomers from commercial poly(ether sulfone) (PES) nanofiltration membranes is developed through a combination of helium and oxygen atmospheric pressure plasma treatment followed by Activators Regenerated by Electron Transfer (ARGET) Atom Transfer Radical Polymerization (ATRP). The resulting membrane surfaces show degree of grafting increases of 28%, 94%, and 270% for methyl methacrylate (C1), hexyl methacrylate (C6), and stearyl methacrylate (C18), respectively, when characterized with Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. Scanning Electron Microscopy and Atomic Force Microscopy (AFM) show a rippled, fibrous morphology for the PES membranes grafted with C18 and reinforced through molecular dynamics simulations. AFM of the PES membranes grafted with C18 show an increase of ~ 23% in root-mean square (RMS) roughness as well as 4x higher adhesion force when probed with a hydrophobic gold cantilever tip when compared with the unmodified PES membranes, confirming a successful surface grafting reaction and increase in surface hydrophobicity, respectively. This technique allows enhanced synthesis of polymer grafted membranes using relatively green reaction solvent and enables “structure-by-design” surface morphology control with future applications in membrane separation processes such as organic solvent nanofiltration, gas separations, and desalination.
Benchmark Electronic Structure Calculations for H 3 O + (H 2 O) n , n = 0–5, Clusters and Tests of an Existing 1,2,3-Body Potential Energy Surface with a New 4-Body Correction
We report a revision of a previously developed many-body (up to 3-body inter- actions) CCSD(T)-based potential energy surface (PES) for the hydrated proton and its extension that incorporates a simple 4-body term for the hydronium-water-water-water interactions. The new PES is parametrized from and tested against new extensive benchmark CCSD(T) Complete Basis Set (CBS) estimates of the binding energies of H3O+(H2O)n clusters, n=0-5, which include all known to date low-lying energy isomers. We report the energetics, structures and harmonic frequencies of the hydronium-water clusters using the PES and compare them against the new benchmarks as well as other best available ab initio results. This critical comparison demonstrates the high accuracy of the new many-body hydronium-water PES.
Charge-Density-Specific Response of Grafted Polyelectrolytes to Electric Fields: Bending or Tilting?
The response of polyelectrolytes (PEs) to applied electric fields drive applications in energetics, diagnostics, materials development, and many more. Here we employ all-atom molecular dynamics (MD) simulations to probe the response of grafted PE brushes to axial electric fields. For PEs with large charge densities, the electric field triggers a left-right asymmetric distribution of counterions around the PE backbone: consequently, depending on the location (left or right), there is an unequal screening and an unequal force on the PE functional groups causing a bending-driven brush height reduction. However, for the weakly charged PEs, the electric field causes a uniform distribution of the counterions across the brush enforcing a uniform (without left-right asymmetry) partially unscreened PE brush: therefore, all the brush segments experience similar force causing a brush tilting-driven brush height reduction. As a result, such bending versus tilting responses is commensurate with the electric-field-driven increase (decrease) in the flexibility of strongly (weakly) charged PEs.