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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Infrared Spectroscopic Observation of Oxo- and Superoxo-Intermediates in the Water Oxidation Cycle of a Molecular Ir Catalyst

Molecular Ir catalysts have emerged as an important class of model catalysts for understanding structure–activity relationships in water oxidation, a reaction that is central to renewable fuel synthesis. Prior efforts have mostly focused on controlling and elucidating the emergence of active species from prepared precursors. However, the development of efficient and stable molecular Ir catalysts also necessitates probing of reaction intermediates. To date, relatively little is known about the key intermediates in the cycles of the molecular Ir catalysts. Herein, we probed the catalytic cycle of a homogeneous Ir catalyst (“blue dimer”) at a Au electrode/aqueous electrolyte interface by combining surface-enhanced infrared absorption spectroscopy (SEIRAS) with phase-sensitive detection (PSD). Cyclic voltammograms (CVs) from 1.4 to 1.7 VRHE (RHE = reversible hydrogen electrode) give rise to a band at ~818 cm –1 , whereas CVs from 1.4 to ≥1.85 VRHE generate an additional band at ~1146 cm –1 . Isotope labeling experiments indicate that the bands at ~818 and ~1146 cm –1 are attributable to oxo (Ir V =O) and superoxo (Ir IV –OO • ) moieties, respectively. Furthermore, this study establishes PSD-SEIRAS as a sensitive tool for probing water oxidation cycles at electrode/electrolyte interfaces and demonstrates that the relative abundance of two key intermediates can be tuned by the thermodynamic driving force of the reaction.

25 ENERGY STORAGE↗
DOE OSTI2021

Organometallic complexes as preferred precursors to form molecular Ir(pyalk) coordination complexes for catalysis of oxygen evolution

Our previously reported ‘blue solution’ oxygen-evolution catalyst consists of an isomeric mixture of coordination complexes containing the (pyalk)Ir IV –O–Ir IV (pyalk) core unit and is thus entirely molecular but only when formed from organometallic precursors such as Cp*Ir(pyalk)Cl or Ir(pyalk)(CO) 2 (pyalk = (2-pyridyl)-2-propanolate). We now show that attempts to form it from such obvious coordination precursors as Na[Ir(pyalk)Cl 4 ] or Na[IrCl 2 (pyalk)(O 2 CPh) 2 ], under a variety of conditions, always fail in our hands, leading to a mixture of molecular ‘blue solution’ species and IrO x nanoparticles, rather than the purely homogeneous catalyst formed from organometallic precursors. The loss of the pyalk ligand during the oxidative activation is associated with the nanoparticle generation. External chelating ligands also failed to stop the nanoparticle formation. This work implies the paradoxical conclusion that organometallic complexes are effective as catalyst precursors, even when coordination complexes are the catalytically active species, since the inner-sphere organometallic ligands, although ultimately lost or degraded, may nevertheless have a stabilizing effect sufficient to suppress undesirable nanoparticle production pathways in the activation of the catalyst precursor. Finally, a key aspect of the present study is that organometallic complexes in general may be useful catalyst precursors even if the organometallic ligands are lost in the activation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

The effects of charged dust grains on IR molecular excitation

A number of issues involving grain charging in the interstellar medium were discussed. Such effects include: (1) stark broadening of molecular spectral features, (2) electrostatic grain rupturing, (3) enhancements in particle-grain collision cross sections, and (4) excitation of molecular rotations and/or vibrations.

Puetter, R.↗
NASA NTRSDate not supplied

Utilizing Experimental-based Line Positions for Semi-empirical IR Line Lists

Molecular IR line lists computed from semi-empirically refined ab initio potential energy surface and high quality ab initio dipole moment surface may have line position accuracy typically within 0.01 - 0.05 cm−1. For high resolution spectroscopy databases, it is necessary to integrate the computed theoretical IR intensities with the line positions accurately determined from experiments and (or) reliably derived from Effective Hamiltonian models. However, it is not a trivial task, and the choices in reality are heavily contingent upon the coverage, consistency, and accuracy of the data available for a specific molecule or isotopologue. We will present several approaches applied to recent Ames IR line lists of CO 2 1, N 2 O 2 , and OCS to demonstrate how challenging such integration may become, and what we have learned From these projects. Discussions will focus on the relation between each different scenario and the corresponding choice or solution, including their advantages and limits, how the semi-empirical IR line lists can help, and what else may be needed for future improvements. We will emphasize that the “Theory+Experiment” synergy may still play significant role in the determination of the best line positions.

Effective Hamiltonian models↗
NASA NTRS1983

Infrared molecular emissions from comets

The possibility of detecting IR molecular line emission from cometary parent molecules is explored. Due to the non-LTE conditions in the inner coma and the large amount of near IR solar flux, IR fluorescence will be a significant source of cometary emission and, in fact, will dominate the grain radiation in a sufficiently high resolution instrument. The detection of this line emission will be difficult due to absorption in the terrestrial atmosphere, but it appears possible to measure cometary H2O emission from airplane altitudes. As IR molecular line emission represents one of the few promising methods of detecting cometary parent molecules directly, further research on this problem should be vigorously pursued.

Weaver, H. A.↗
NASA NTRS1984

Infrared molecular emissions from comets

The possibility of detecting IR molecular line emission from cometary parent molecules is explored. Due to the non-LTE conditions in the inner coma and the large amount of near IR solar flux, IR fluorescence will be a significant source of cometary emission and, in fact, will dominate the grain radiation in a sufficiently high resolution instrument. The detection of this line emission will be difficult due to absorption in the terrestrial atmosphere, but it appears possible to measure cometary H2O emission from airplane altitudes. As IR molecular line emission represents one of the few promising methods of detecting cometary parent molecules directly, further research on this problem should be vigorously pursued. Previously announced in STAR as N83-30344

Weaver, H. A.↗
NASA NTRS1992

The molecular hydrogen emission around L1551 IRS 5 - Shock-heated molecular gas at the base of the molecular outflow

Spatially resolved observations of the v = 1-0 S(1) molecular hydrogen emission toward L1551 IRS 5 using the grating spectrometer at KPNO are presented. The S(1) emission consists of a ridge component extending toward west along the optical jet from its peak on IRS 5 and a diffuse component which traces the innermost region of the cavity enclosed by the molecular outflow. The ridge component represents shock-heated molecular gas at the root of the optical jet. The diffuse component is too bright to be of scattered origin; it most likely arises from shock-heated gas within the cavity and could represent an acceleration process of the molecular outflow.

Yamashita, Takuya↗
DOE OSTI2023

Electrolyte Engineering Stabilizes Photoanodes Decorated with Molecular Catalysts

Molecular catalysts are promising oxygen evolution promoters in conjunction with photoanodes for solar water splitting. Maintaining the stability of both photoabsorber and cocatalyst is still a prime challenge, with many efforts tackling this issue through sophisticated material designs. Such approaches often mask the importance of the electrode-electrolyte interface and overlook easily tunable system parameters, such as the electrolyte environment, to improve efficiency. We provide a systematic study on the activity-stability relationship of a prominent Fe 2 O 3 photoanode modified with Ir molecular catalysts using in situ mass spectroscopy. After gaining detailed insights into the dissolution behavior of the Ir cocatalyst, a comprehensive pH study is conducted to probe the impact of the electrolyte on the performance. An inverse trend in Fe and Ir stability is found, with the best activity-stability synergy obtained at pH 9.7. The results bring awareness to the overall photostability and electrolyte engineering when advancing catalysts for solar water splitting.

14 SOLAR ENERGY↗
DOE OSTI2020

Strong mutual increase in the efficiency of isotope-selective laser IR dissociation of molecules under nonequilibrium thermodynamic conditions of the compression shock under irradiation in a bimolecular mixture

We have revealed a strong (by a factor of 2 to 5) mutual increase in the yield of IR molecular dissociation (by the example of CF{sub 2}HCl and CF{sub 3}Br) and a significant (by a factor of 1.5 to 3) lowering of dissociation thresholds in the nonequilibrium thermodynamic conditions of compression shock in the irradiation of the molecules by resonance IR laser radiation in the bimolecular mixture in comparison with their individual irradiation. This opens up the possibility to perform efficient isotope-selective IR dissociation of molecules at lower excitation energy densities (Φ ⩽ 1.5 – 2.0 J cm{sup −2}) and thereby to improve the dissociation selectivity. This was demonstrated by the example of chlorine- and bromine-isotope selective dissociation of the specified molecules, which are characterised by quite small (less than 0.25 cm{sup −1}) isotope shifts in the IR vibrational absorption spectra excited by laser radiation. The enrichment coefficients K {sub enr}({sup 35}Cl / {sup 37}Cl) = 0.90 ± 0.05 in the residual CF{sub 2}HCl gas and K {sub enr}({sup 79}Br / {sup 81}Br) in the resultant Br{sub 2} product are obtained when the CF{sub 2}HCl : CF{sub 3}Br = 1 : 1 molecular mixture and CF{sub 3}Br molecules, respectively, are irradiated by the 9R(30) CO{sub 2} laser line (frequency, 1084.635 cm{sup −1}) at an energy density Φ ≈ 1.3 J cm{sup −2}. (laser isotope separation)

36 MATERIALS SCIENCE↗
NASA NTRS1990

Dust around AFGL 2688, molecular shielding, and the production of carbon chain molecules

The molecular, IR, and optical maps of the evolved carbon star AFGL 2688 (the 'Egg' Nebula) are all consistent with a model of a bipolar outflow of approximately 0.0001 solar masses/yr that stopped as this object evolved beyond the asymptotic giant branch about 200 years ago. In order to explain the extended HC7N emission around this star, it is proposed that carbon grains are collisionally fragmented as they supersonically steam through the circumstellar envelope.

Jura, M.↗
NASA NTRS1991

Advanced Si IR detectors using molecular beam epitaxy

SiGe/Si heterojunction internal photoemission (HIP) long wavelength infrared (LWIR) detectors have been fabricated by MBE. The SiGe/Si HIP detector offers a tailorable spectral response in the long wavelength infrared regime by varying the SiGe/Si heterojunction barrier. Degenerately doped p(+) SiGe layers were grown using elemental boron, as the dopant source allows a low growth temperature. Good crystalline quality was achieved for boron-doped SiGe due to the reduced growth temperature. The dark current density of the boron-doped HIP detectors was found to be thermionic emission limited. HIP detectors with a 0.066 eV were fabricated and characterized using activation energy analysis, corresponding to a 18 micron cutoff wavelength. Photoresponse of the detectors at wavelengths ranging from 2 to 12 microns has been characterized with corresponding quantum efficiencies of 5 - 0.1 percent.

Lin, T. L.↗
NASA NTRS2019

Isotopologue Consistency of Semi-Empirically Computed InfraRed Line Lists and Further Improvement for Rare Isotopologues: CO2 and SO2 Case Studies.

The semi-empirical molecular rovibrational IR line lists, such as ExoMol, TheoReTs, and Ames, combine the experimental accuracy and theoretical power to reach better than 0.1 cm-1 accuracy for line positions and better than 80-90% agreement for line intensities. The quality of these existing semi-empirical IR lists allows further improvements of intensity and line positions for those unobserved minor isotopologues. This paper presents our new BTRHE (Best Theory + Reliable High-resolution Experiment) strategy implementation. For line intensity, the isotopologue consistency and the patterns of mass dependence in the Ames-296K SO2 and CO2 IR lists are quantitatively presented along the mass-inverse coordinates. The consistency and patterns are better than those in existing experimental data. The methodology proposed here can be used to identify inconsistencies, outliers, and mistakes in intensities, and help improve Effective Dipole Model (EDM) and molecular IR databases. We call for an experimental study on the 50006 and 60007 bands of CO2 628. For line position predictions, a simple approach combining the variational IR line lists with Effective Hamiltonian (EH) model may refine the effective rotational constants A0/B0/C0 and quartic centrifugal distortion constants of minor isotopologues. The prediction accuracy may be improved by two orders of magnitude, i.e. reaching 0-5 MHz prediction accuracy in the range of J<20-30, Ka<10-20, and 0.01-0.02 MHz accuracy for A0/B0/C0. Several important factors have been systematically investigated and discussed, e.g. convergence, uncertainties, higher order terms, fixing EH parameters, mass coordinates, etc. Amicrowave (MW) line set consisting of 644,636 strong transitions for all 30 isotopologues and corresponding refined EH(Ames) parameters are reported in the supplementary material. This approach may be easily extended to rovibrational bands, hot bands, and other molecular systems.

Xinchuan Huang↗
DOE OSTI2025

Assessing the Effect of Explicit Polarizability on Models of Carbon Dioxide Solvation in Ionic Liquids

Ionic liquids are an important possible carbon capture material because of their anomalously high sorption selectivity for carbon dioxide over other gases common in air. Many research groups have investigated the molecular origins of this property and provided important insights, including using 1D and 2D-IR spectroscopy. Molecular dynamics simulations have been indispensable to the interpretation of these experiments. In prior molecular dynamics simulation work, charge-scaled force fields have typically been used to provide a mean-field treatment of effects vital to ionic liquid systems such as charge transfer and polarization. Here, we compare models of carbon dioxide solvated in ionic liquids with explicit polarization to models of the same with implicit polarizability through charge-scaling. We calculate structural, dynamical, and spectroscopic properties, and make comparisons to the same items measured in experiment. In this study, we focus on two ionic liquids: 1-butyl-3- methylimidazolium (BMIM + ) paired with bis(trifluoromethane sulfonyl imide) (Tf 2 N − ) and 1-butyl-3-methylimidazolium (BMIM+) paired with hexafluorophosphate (PF 6 − ). We find that many structural, dynamical, and spectroscopic properties are changed when polarization is modeled explicitly. We also find that explicit polarizability softens local ion cages around the carbon dioxide and that the long-time diffusion of the carbon dioxide is gated by the reorganization of the ionic liquid molecules. Comparisons to experiment show modest improvement of many observables compared with experiment for the explicitly polarizable model over the charge-scaled model. Overall, our results show that charge-scaled force fields are likely sufficient to compute spectroscopic properties of carbon dioxide in ionic liquids and suggest some interpretive rules for understanding their structural and dynamical properties. Those using charge-scaled force fields should generally assume that the ion cages around solutes such as carbon dioxide are too stiff and cation-rich in their models and adjust their interpretations and predictions accordingly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

Dust reradiation from M43

Far-IR and molecular observations of M43 and its neutral environment are presented. Dust particles mixed with plasma, atoms, and molecules of the observed region are found to produce the measured far-IR emissions. M43 and its neutral environment have a simple morphology, consisting primarily of a relatively dust-free H II region and its centrally located exciting star lying next to the dense concentration of neutral material known as the Orion Ridge. The exciting star, NU Ori, is an important source of excitation of the dust associated with M43. Dust mixed with gas lying along or outside the near circular boundary of M43 is important for the energy balance of the M43 region. The amount of far-IR reradiation observed from the central 1 arcmin of M43 is equivalent to only about one percent of the NU Ori luminosity. a fraction implying a small value for the normalized absorption optical depth. This may partly explain why extinction by dust appears to have little effect on the excitation of the M43 plasma.

Smith, J.↗
NASA NTRS1997

Novel Spectrograph/Radiometer for Cloud Top Height Measurement Using Three Complementary Techniques

A proof-of-concept (POC) instrument system to measure cloud top height from space using three complementary techniques is presented. These techniques use measurements of: (1) thermal infrared (IR); (2) molecular oxygen 'A' band absorption; and (3) filling-in of Fraunhofer lines (the Ring effect), respectively. Combining three techniques is achieved with a single grating spectrograph with bandpass and order sorting filters by measuring I I jim radiation from the zeroth order of the grating for the IR, 750-780 nm radiation from the first order for the 'A' band absorption, and 390-400 mn radiation from the second order for the Ca K and H Fraunhofer line filling-in effect. The POC system and its measurement results with the POC system are described.

Park, Hongwoo↗