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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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Chemical effects in X-ray spectra and inner shell photoelectron spectra of sulfur- and chlorine- oxygen anions and molecular orbital method
Molecular orbital electron charge density pictures, noting representation close to Hartree-Fock calculation method
Experimental and theoretical studies disagree on the energetics of methane adsorption on carbon materials. However, this information is critical for the rational design and optimization of the structure and composition of adsorbents for natural gas storage. The delicate nature of dispersion interactions, polarization of both the adsorbent and the adsorbate, interplay between H-bonding and tetrel bonding, and induced dipole/Coulomb interactions inherent to methane physisorption require computational treatment at the highest possible level of theory. In this study, we employed the smallest reasonable computational model, a maquette of porous carbon surfaces with a central site for substitution and methane binding. The most accurate predictions of methane adsorption energetics were achieved by electron-correlated molecular orbital theory CCSD(T) and hybrid density functional theory MN15 calculations employing a saturated, all-electron basis set. Here, the characteristic geometry of methane adsorption on a carbon surface (“lander approach”) arises due to bonding interactions of the adsorbent π-system with the proximal H–C bonds of methane, in addition to tetrel bonding between the antibonding orbital of the distal C–H bond and the central atom of the maquette (C, B, or N). The polarization of the electron density, structural deformations, and the comprehensive energetic analysis clearly indicate a ∼3 kJ mol –1 preference for methane binding on the N-substituted maquette. The B-substituted maquette showed a comparable or lower binding energy than the unsubstituted, pure C model, depending on the level of theory employed. The calculated thermodynamic results indicate a strategy for incorporating electron-enriched substitutions (e.g., N) into carbon materials as a way to increase methane storage capacity over electron-deficient (e.g., B) modifications. The thermochemical analysis was revised for establishing a conceptual agreement between the experimental isosteric heat of adsorption and the binding enthalpies from statistical thermodynamics principles.
Energy required for proton and molecular hydrogen ion production by electron impact in tenuous hydrogen plasma using Maxwellian electron gas model
We investigate the surface electronic structure of SrTiO3 (STO) films grown by a hybrid molecular beam epitaxy that are both stoichiometric and nonstoichiometric by means of x-ray photoelectron spectroscopy and electron energy loss spectroscopy. Increasing the fraction of the surface that is terminated with an SrO layer is correlated with a decrease in the chemical potential whereby the valence band maximum moves closer to the Fermi level, but without a significant change in the bandgap. Inasmuch as SrO-terminated STO (001) has previously been shown to act as an electron scavenger in which carriers from the bulk are trapped, we argue that the high fraction of SrO in the terminal layer is what lowers the chemical potential in Sr-rich STO. Our experimental results provide important insights into various physical phenomena that can occur on STO (001) surfaces and their effect on bulk electronic properties.
Optical spectra of molecular emissions during electron bombardment of acetylene
We report a study aimed at understanding analyte interactions with sensors made from polymer-carbon black composite films. The sensors are used in an Electronic Nose (ENose) which is used for monitoring the breathing air quality in human habitats. The model mimics the experimental conditions of the composite film deposition and formation and was developed using molecular modeling and simulation tools. The Dreiding 2.21 Force Field was used for the polymer and analyte molecules while graphite parameters were assigned to the carbon black atoms. The polymer considered for this work is methyl vinyl ether / maleic acid copolymer. The target analytes include both inorganic (NH3) and organic (methanol) types of compound. Results indicate different composite-analyte interaction behavior.
In this paper, we present CTRAMER (Charge-Transfer RAtes from Molecular dynamics, Electronic structure, and Rate theory)—an opensource software package for calculating interfacial charge-transfer (CT) rate constants in organic photovoltaic (OPV) materials based on ab initio calculations and molecular dynamics simulations. The software is based on identifying representative donor/acceptor geometries within interfacial structures obtained from molecular dynamics simulation of donor/acceptor blends and calculating the corresponding Fermi’s golden rule CT rate constants within the framework of the linearized-semiclassical approximation. While the methods used are well established, the integration of these state-of-the-art tools originating from different disciplines to study photoinduced CT processes with explicit treatment of the environment, in our opinion, makes this package unique and innovative. The software also provides tools for investigating other observables of interest. After outlining the features and implementation details, the usage and performance of the software are demonstrated with results from an example OPV system.
Optical spectra of molecular emissions during electron bombardment of methane
The electronic or molecular mechanisms which initiate photobiomodulation (PBM) in cells are not yet fully understood. Porcine complex III (C-III) of the electron transport chain was characterized with transient absorption spectroscopy (TAS). Then we applied our recently developed continuous wave laser coupled TAS procedure (CW-TAS) to investigate the effect of red light irradiances on the heme dynamics of C-III in its c 1 reduced state. The time constants associated with the axial ligand photodissociation were found to be 3.3 ± 0.3 ps for the oxidized state and 4.9 ± 0.4 ps for the c 1 reduced state. The analysis of the CW-TAS procedure yielded no significant changes in the C-III heme dynamics. We rule out the possibility of 635 nm CW light at 4.7 mW/cm 2 inducing a PBM effect on the heme dynamic of C-III, specifically with the photodissociation of its axial ligand.
We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL electronic nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereoisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings with no hydrogens. The Dreiding 2.21 force field is used for the polymer, solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4-vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic and organic compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites. c2003 Elsevier Science B.V. All rights reserved.
Dissociation and reassociation reactions of hemocyanin mixtures analyzed by electron microscopy, noting original molecular structures
By electron spectroscopy it was shown that aromatic polyimides containing electron-donor residues of diamines -C6H4-X-C6H-(X=NH, NCH3, NC6H5, O, S, and CH2) form charge transfer complexes with low-molecular-weight electron acceptors. Based on the data obtained, the hypothesis was advanced that the coloration of the polyimides per se is due to the formation of charge transfer complexes between the electron-acceptor imide fragments and the electron-donor residues of the diamines.
A crossed molecular beam-electron beam apparatus was employed to examine the excitation cross-sections of CH4. Attention was given to 20, 30, and 200 eV impact energies at angles from 8-130 deg. Spectra were obtained in the elastic and inelastic realms as well as in the ionization continuum in the 12.99-15.0 eV energy-loss range. Differential cross-sections were also determined. The results are useful for modeling the behavior of CH4 in planetary atmospheres.
We report on a new water-soluble cobalt( II ) complex capable of water splitting bifunctionality, i.e., water reduction and water oxidation. The species [Co II (L Qpy )H 2 O]ClO 4 (1), where L Qpy is the deprotonated form of the new tripodal ligand N 1 ,N 1 -bis(pyridin-2-ylmethyl)-N 2 -(quinolin-8-yl)benzene-1,2-diamine, HL Qpy , was developed aiming to replace an oxidation prone methylene group by a sturdy and redox stable quinoline. The molecular and electronic structures of 1 were evaluated by multiple spectroscopic, spectrometric, electrochemical and computational methods, and detailed pre- and post-catalytic studies were conducted to ascertain the molecular nature of the conversions. Complex 1 performs water reduction at a low onset overpotential (η) of 0.65 V at pH 7, reaching TON 3h 2900 (TOF 970 h −1 ) and TON 18h 12 100 (TOF 672 h −1 ) with up to 98% faradaic efficiency (FE). Species 1 also promotes water oxidation at η = 0.34 V under pH 8, achieving TON 3h 193 (TOF 64 h −1 ) at 84% FE. Experimental and DFT results enabled us to propose reaction intermediates and mechanisms.
Specialized computational chemistry packages have permanently reshaped the landscape of chemical sciences by providing tools to support and guide the experimental effort and for prediction of chemical and materials properties. In this regard, a special role has been played by electronic structure packages where complex chemical and materials processes can be modeled using first-principle-driven methodologies. Over the last few decades, the rapid development of computing technologies and a tremendous increase in computational power has offered a unique chance to study complex chemical transformations using sophisticated and predictive many-body techniques to describe correlated behavior of electrons in molecular and condensed phase systems at different levels of theory. In enabling these simulations, a critical role has been played by novel parallel algorithms capable of taking advantage of computational resources to address polynomial scaling of electronic structure methods. NWChem was among the first electronic structure codes that focused on delivering scalable performance for electronic structure simulations. Herein, we briefly review the NWChem suite of computational codes including its history, design principles, parallel tools, current capabilities, outreach and outlook.
Energy requirements for proton production by electron impact of hydrogen plasma
Molecular nitrogen excitation under electron bombardment at auroral and airglow impact levels, using computerized Monte Carlo method