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NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

Hydrogen cyanide (HCN) is found in a wide variety of extraterrestrial environments within and beyond the solar system, and for that reason laboratory spectroscopists have studied this compound in many spectral regions, including the infrared (IR). However, one aspect that remains to be investigated is the intrinsic IR spectral intensities of solid HCN as opposed to relative band strengths, intrinsic intensities being needed to measure HCN abundances. Here we report measurements of IR absorption coefficients and band strengths, along with supporting refractive indices and densities, of both amorphous and crystalline HCN at two temperatures, one for interstellar work and one more relevant to the outer solar system. Spectra are presented at both temperatures, along with optical constants that can be used in numerical models. Despite widespread and longstanding interest in and investigations of solid HCN, this is the first time that the properties we are reporting have been measured in a single laboratory, avoiding the need for estimates or to combine results from various authors. We find that our measured band strength of ~1 × 1017 cm molecule1 for the CN vibration of HCN, in both amorphous HCN and in an H2O-rich ice, is substantially higher than an earlier estimate. Unless errors of 100% can be tolerated then our new value requires a rescaling of earlier work. Our results shed light on why HCN and other nitriles have been so difficult to identify in the solid state, in contrast to their many detections in the gas phase.

astrochemistry – methods: laboratory – solid state↗

NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

astrochemistry – methods: laboratory – solid state↗

DOE OSTI2026

Spectroscopy and dynamics of the v = 1 levels derived from the OH(D) stretching modes in the I‾∙HDO complex using CW and time-resolved, resonant two-photon infrared excitation of the cryogenically cooled ions

The vibrational energy levels of the two isotopomers adopted by the I‾∙HDO ion-molecule complex occur such that the OH(D) stretching fundamentals span its dissociation energy, thus enabling a spectroscopic investigation of the dynamics displayed by a system prepared in the vicinity of the dissociation threshold. This regime is explored using infrared photoexcitation of the mass-selected complexes cooled in a cryogenic radiofrequency (Paul) ion trap. Survey spectra are obtained at modest resolution using two-color, IR-IR photodissociation with nanosecond lasers to establish the level structure and unimolecular decay dynamics of the v = 1 and 2 levels of the bound OH(D) oscillator. The v = 1 levels are prepared by fixed frequency excitation in the trap and the absorption spectra arising from this excited state are probed by photofragmentation of the complex with a second pulsed IR laser after a variable delay time (0 to 20 ms). The transitions to levels above the dissociation threshold for I‾ + HDO formation are observed to be sharp (~5 cm -1 FWHM). At low pressure, the bound OD (v = 1) population relaxes very slowly (~3 ms), consistent with resonant fluorescence in the IR. The collisional quenching rate constants of this level by the He buffer gas were estimated to be on the order 3 x 10 -12 cm 3 /s based on a crude Stern-Volmer analysis. Here, the rotational fine structure and linewidths (≲0.01 cm -1 FWHM) arising from transitions of the non-bonded OH stretch fundamental of the OD-bound isotopomer that lies just above the dissociation energy are determined using single photon photodissociation by excitation of the 10 K ions with a single-frequency, CW IR laser in the ion trap.

Cryogenic ion infrared spectroscopy↗

NASA NTRS2018

The Star-Grazing Bodies in the HD 172555 System

Kiefer et al. reported the detection of in falling Ca(sub II) absorption in HD 172555, a member of the β Pictoris Moving Group (βPMG). We obtained HST Space Telescope Imaging Spectrograph and Cosmic Origins Spectrograph spectroscopy of this star at 2 epochs separated by a week, and we report the discovery of infalling gas in resonant transitions of Si(sub III and IV), C(sub II and IV), and neutral atomic oxygen. Variable absorption is seen in the C(sub II) transitions and is optically thick, with covering factors which range between 58% and 68%, similar to features seen in β Pictoris. The O(sub I) spectral profile resembles that of C(sub II), showing a strong low-velocity absorption to +50 km s(exp −1) in the single spectral segment obtained during orbital night, as well as what may be higher-velocity absorption. Studies of the mid-IR spectrum of this system have suggested the presence of silica. The O(sub I) absorption differs from that seen in Si(sub III), suggesting that the neutral atomic oxygen does not originate in SiO dissociation products but in a more volatile parent molecule such as CO.

HST Space Telescope Imaging Spectrograph↗

DOE OSTI2022

Solvent-Driven Transformation of Zn/Cd 2+ -Deoxycholate Assemblies

Deoxycholic acid (DOC) is a unique, biologically derived surfactant with facial amphiphilicity that has been exploited, albeit minimally, in supramolecular assembly of materials. Here, we present the synthesis and structural characterization of three hybrid metal (Zn 2+ and Cd 2+ )-DOC compounds. Analysis by single-crystal Xray diffraction reveals the many interactions that are possible between these facial surfactants and the influence of solvent molecules that drive the assembly of materials. These structures are the first metal- DOC complexes besides those obtained from alkali and alkaline earth metals. We isolated polymeric chains of both Cd and Zn (Zn poly -DOC and Cd poly -DOC) from water. Major interactions between DOC molecules in these phases are hydrophobic in nature. Cd poly -DOC exhibits unique P1 symmetry, with complete interdigitation of the amphiphiles between neighboring polymeric chains. Zn 4 -DOC, obtained from methanol dissolution of Zn poly -DOC, features the OZn 4 tetrahedron, widely known in basic zinc acetate and MOF-5 (metal organic framework). We document a solvent-driven, roomtemperature transition between Zn poly -DOC and Zn 4 -DOC (in both directions) by scanning and transmission electron microscopies in addition to small-angle X-ray scattering, powder X-ray diffraction, and infrared spectroscopy. These studies show the methanoldriven transition of Zn poly -DOC to Zn 4 -DOC occurs via an intermediate with no long-range order of the Zn 4 clusters, indicating the strongest interactions driving assembly are intramolecular. On the contrary, water-driven solid-to-solid transformation from Zn 4 -DOC to Zn poly -DOC exhibits crystal-to-crystal transformation. Zn poly -DOC is robust, easy to synthesize, and comprised of biologically benign components, so we demonstrate dye absorption as a proxy for water treatment applications. It favors absorption of positively charged dyes. These studies advance molecular level knowledge of the supramolecular assembly of facial surfactants that can be exploited in the design of organic-inorganic hybrid materials. This research also highlights the potential of solvent for tuning supramolecular assembly processes, leading to new hybrid materials featuring facial surfactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2017

Molecular Composition Analysis of Distant Targets

This document is the Final Report for NASA Innovative Advanced Concepts (NIAC) Phase I Grant 15-NIAC16A-0145, titled Molecular Composition Analysis of Distant Targets. The research was focused on developing a system concept for probing the molecular composition of cold solar system targets, such as Asteroids, Comets, Planets and Moons from a distant vantage, for example from a spacecraft that is orbiting the target (Hughes et al., 2015). The orbiting spacecraft is equipped with a high-power laser, which is run by electricity from photovoltaic panels. The laser is directed at a spot on the target. Materials on the surface of the target are heated by the laser beam, and begin to melt and then evaporate, forming a plume of asteroid molecules in front of the heated spot. The heated spot glows, producing blackbody illumination that is visible from the spacecraft, via a path through the evaporated plume. As the blackbody radiation from the heated spot passes through the plume of evaporated material, molecules in the plume absorb radiation in a manner that is specific to the rotational and vibrational characteristics of the specific molecules. A spectrometer aboard the spacecraft is used to observe absorption lines in the blackbody signal. The pattern of absorption can be used to estimate the molecular composition of materials in the plume, which originated on the target. Focusing on a single spot produces a borehole, and shallow subsurface profiling of the targets bulk composition is possible. At the beginning of the Phase I research, the estimated Technology Readiness Level (TRL) of the system was TRL-1. During the Phase I research, an end-to-end theoretical model of the sensor system was developed from first principles. The model includes laser energy and optical propagation, target heating, melting and evaporation of target material, plume density, thermal radiation from the heated spot, molecular cross section of likely asteroid materials, and estimation of the absorption profile at a distant spectrometer. Results obtained by executing simulations based on the model provide compelling evidence that the concept of remote laser evaporative molecular absorption spectroscopy is feasible. In this document, technical details of the model are presented, and results of simulations are described that indicate the utility of the proposed sensor system. Additionally, an asteroid rendezvous mission is analyzed, with a survey of system requirements to accomplish molecular composition analysis of the asteroid. Based on positive theoretical results obtained during Phase I, the estimated TRL of the system is now TRL-2. This document also describes potential future research and experimentation that could push the system to TRL-4 within 2 years. Steps required for construction of a laboratory prototype are described. An experiment to test predictions of the theory is described, based on the laboratory prototype setup.

asteroid↗

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 OSTI2023

Excited-State Dynamics during Primary C–I Homolysis in Acetyl Iodide Revealed by Ultrafast Core-Level Spectroscopy

In typical carbonyl-containing molecules, bond dissociation events follow initial excitation to $nπ_{C=O}$$^*$ states. However, in acetyl iodide, the iodine atom gives rise to electronic states with mixed $nπ_{C=O}$$^*$ and $nπ_{C–I}$$^*$ character, leading to complex excited-state dynamics, ultimately resulting in dissociation. Using ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy and quantum chemical calculations, we present an investigation of the primary photodissociation dynamics of acetyl iodide via time-resolved spectroscopy of core-to-valence transitions of the I atom after 266 nm excitation. The probed I 4d-to-valence transitions show features that evolve on sub-100-fs time scales, reporting on excited-state wavepacket evolution during dissociation. These features subsequently evolve to yield spectral signatures corresponding to free iodine atoms in their spin–orbit ground and excited states with a branching ratio of 1.1:1 following dissociation of the C–I bond. Calculations of the valence excitation spectrum via equation-of-motion coupled cluster with single and double substitutions (EOM-CCSD) show that initial excited states are of spin-mixed character. From the initially pumped spin-mixed state, we use a combination of time-dependent density functional theory (TDDFT)-driven nonadiabatic ab initio molecular dynamics and EOM-CCSD calculations of the N$_{4,5}$ edge to reveal a sharp inflection point in the transient XUV signal that corresponds to rapid C–I homolysis. Here, by examining the molecular orbitals involved in the core-level excitations at and around this inflection point, we are able to piece together a detailed picture of C–I bond photolysis in which d → σ* transitions give way to d → p excitations as the bond dissociates. We also report theoretical predictions of short-lived, weak 4d → 5d transitions in acetyl iodide, validated by weak bleaching in the experimental transient XUV spectra. This joint experimental–theoretical effort has thus unraveled the detailed electronic structure and dynamics of a strongly spin–orbit coupled system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2002

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR studies (telescopic and laboratory) have demonstrated that much of the carbon in the interstellar medium (ISM) is in complex organic species of a variety of types, but the distribution, abundance, and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEAST mission concept designed to conduct IR spectroscopic observations to detect and identify these materials to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. Systematic studies include the observation of planetary nebulae and stellar outflows, protostellar objects, Solar System Objects, and galaxies, and multiple lines of sight through dense molecular clouds and the diffuse ISM. ABE will also search for evidence of D enrichment in complex molecules in all these environments. The mission is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cryogenic cross-dispersed spectrographs that share a single common slit. The 3 spectrometers each measure single spectral octaves (2.5-5, 5-10, 10-20 microns) and together cover the entire 2.5 - 20 micron region simultaneously. The spectrometers use state-of-the-art 1024x1024 pixel detectors, with a single InSb array for the 2.5-5 micron region and two Si:As arrays for the 5-10 and 10-20 micron regions. The spectral resolution is wavelength dependent but is greater than 2000 across the entire spectral range. ABE would operate in a heliocentric, Earth drift-away orbit and is designed to take maximum advantage of this environment for cooling, thermal stability, and mission lifetime. ABE would have a core science mission lasting approximately 1.5 years.

Sandford, Scott A.↗

DOE OSTI2024

Resonant Auger decay of iodobenzene below the I 4d edge

New data are presented on the resonant Auger decay of iodobenzene (C 6 H 5 I) in the region of the I 4d –1 ionization threshold. The excited molecules decay by participator and spectator processes to populate single-hole valence states and two-hole, one-particle excited states of the cation, providing new information on the structure of C 6 H 5 I + . Excitation of dissociative C 6 H 5 I (I 4d 5/2,3/2 –1 )σ* resonances can, in principle, result in ultrafast dissociation to C 6 H 5 + I** and the subsequent autoionization of I**, but no evidence for this process is observed. Finally, the results are compared with our recent study of the resonant Auger decay of methyl iodide (CH 3 I).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Title Coherent X-ray Studies of Surface Growth and Patterning Processes

X-ray Photon Correlation Spectroscopy (XPCS) is being developed as a tool to study nanoscale dynamics of fluctuations during thin film growth and surface patterning. XPCS examines the evolution of the X-ray scattering speckle pattern in reciprocal space to reveal dynamics information not accessible through any other means. Unlike low-coherence conventional X-ray scattering, which incoherently averages over different regions of a sample, coherent X-ray scattering is sensitive to the detailed structure of a given sample at that moment in time. In thin film growth processes, heterodyning, which occurs due to coherent mixing of two scattered signals, can be used to investigate the relationship between surface growth velocity and defect propagation. And, for polycrystalline thin film growth, the spatial coherence of the X-ray beam can substitute for the missing spatial coherence of the growth process to track layered growth in detail, even in a growth regime in which there are no conventional growth oscillations of the X-ray intensity. This has opened the door for detailed dynamics studies of individual atomic layers during real-world growth and patterning, not just in perfect single-crystal growth cases, which greatly expands the applicability of in-situ X-ray scattering methods. Step-flow dynamics in mounded polycrystalline growth has been studied separately for two thin film organic semiconductors deposited by thermal deposition in a vacuum environment, C60 and diindenoperylene (DIP). Highly oriented polycrystalline thin films are readily obtained in both systems, where mounds are composed of crystalline monolayer-height steps and terraces in a so-called wedding cake morphology. The formation of mounds is understood to be due to significant Ehrlich-Schwoebel step edge barriers that inhibit molecules from hopping down from one layer to the one below. The mounds exhibit local step flow, which can be monitored using coherent X-ray scattering. This is made possible due to heterodyning between scattering from the average mounds and the moving steps, which becomes visible in XPCS analysis. The effect of desorption, i.e. re-evaporation of deposited molecules is found to be important for understanding these processes. The impact of this work is to enable testing of models of step dynamics, the shape of mounds, and merging of mounds to form continuous thin films. Highly ordered polycrystalline thin films deposited on inexpensive substrates have applications in thin film solar cells and other organic electronic devices. In a separate set of experiments, speckle analysis during self-organized ion beam nanopatterning reveals memory stretching back to the beginning of patterning in the early stages and enables measurement of the velocity of self-organized patterns across surfaces providing the possibility of stringent new tests of the theory of pattern formation and motion.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Investigation of Mass Transfer and Sorption in CO 2 /Brine/Rock Systems via In Situ FT-IR

CO 2 geological storage in deep saline formations is considered a promising method to mitigate anthropogenic CO 2 emissions and, thereby, minimize changes to the Earth’s atmosphere. A fundamental understanding of CO 2 mass transfer and sorption phenomena in brine-saturated reservoir formations is necessary to understand the long-term fate of injected CO 2 as it is subjected to different (physical, dissolution, and mineral) trapping mechanisms. In this work, we investigate CO 2 sorption in brine-saturated and dry Mt. Simon sandstone samples via in-situ Fourier Transform infrared spectroscopy (FT-IR) at elevated pressures, ranging from 0.3 MPa to 8.3 MPa, at a temperature of 50 ⁰C. The FT-IR spectra of bulk-phase CO 2 were simultaneously recorded under the same conditions. For bulk-phase CO 2 , we observed, in agreement with past studies, a doublet peak at 2361 cm -1 and 2336 cm -1 and another peak (ν 2 bending mode) at 667 cm -1 . With increasing pressure, the position of the peak at 667 cm -1 remains invariant, however, when crossing into the supercritical region the doublet peak degenerates onto a single peak at 2336 cm -1 with a barely visible shoulder at 2361 cm -1 . The bulk CO 2 data provide a perfect fit for Beer’s law for the whole range of pressure conditions. For the dry sample, the IR spectrum is experimentally indistinguishable from the bulk CO 2 spectrum, signifying that if physical adsorption occurs to any significant extent, the adsorbed CO 2 molecules are not substantially more rotationally constrained than the dense bulk CO 2 molecules. For the brine-saturated sample, we observe a strong band centered at 2342 cm -1 and a small companion peak at 2360-2361 cm -1 that degenerates into a barely visible shoulder peak at the higher pressures. The 2342 cm -1 band has been previously observed by other investigators for CO 2 dissolved in bulk water/brine as well during its adsorption on a variety of other wet natural porous media. We observe no peaks corresponding to bicarbonate or carbonate bulk species, which correlates well with the prior literature on similar low-pH aqueous solutions. The integrated peak area for the CO 2 sorbed in the brine-saturated sample correlates linearly with its solubility in the same bulk brine, as measured separately via a PVT-cell approach. Here, this validates the accuracy of both techniques, and the potential of the FT-IR method to be used in the study of mass transfer and adsorption in such systems. To that effect, a simple mathematical model is presented to analyze the FT-IR data to determine the CO 2 effective diffusivity in the brine-saturated sandstone sample.

58 GEOSCIENCES↗

DOE OSTI2021

Strong-field ionization of water. II. Electronic and nuclear dynamics en route to double ionization

We investigate the role of nuclear motion and strong-field-induced electronic couplings during the double ionization of deuterated water using momentum-resolved coincidence spectroscopy. By examining the three-body dicationic dissociation channel, D$^{+}$/D$^{+}$/O, for both few- and multi-cycle laser pulses, strong evidence for intra-pulse dynamics is observed. The extracted angle- and energy-resolved double ionization yields are compared to classical trajectory simulations of the dissociation dynamics occurring from different electronic states of the dication. In contrast with measurements of single photon double ionization, pronounced departure from the expectations for vertical ionization is observed, even for pulses as short as 10~fs in duration. We outline numerous mechanisms by which the strong laser field can modify the nuclear wavefunction en-route to final states of the dication where molecular fragmentation occurs. Specifically, we consider the possibility of a coordinate-dependence to the strong-field ionization rate, intermediate nuclear motion in monocation states prior to double ionization, and near-resonant laser-induced dipole couplings in the ion. These results highlight the fact that, for small and light molecules such as D$_2$O, a vertical-transition treatment of the ionization dynamics is not sufficient to reproduce the features seen experimentally in the strong field coincidence double-ionization data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2022

State-selective probing of CO 2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy

Nonlinear spectroscopies can disentangle spectra that are congested due to inhomogeneous broadening. Here, in conjunction with theoretical calculations, attosecond extreme ultraviolet (XUV) four-wave-mixing (FWM) spectroscopy is utilized to probe the dynamics of autoionizing inner valence excited Rydberg states of the polyatomic molecule, CO 2 . This tabletop nonlinear technique employs a short attosecond XUV pulse train and two noncollinear, few-cycle near-infrared pulses to generate background-free XUV wave-mixing signals. FWM emission is observed from the n=5-7 states of the Henning sharp ndσ g Rydberg series that converges to the ionic $\widetilde{B}$ 2 Σ$^{+}_{u}$ state. However, these transient emission signals decay with lifetimes of 33 ± 6, 53 ± 2, and 94 ± 2 fs, respectively, which calculations show are consistent with the lifetimes of the short-lived n=6-8 members of the nsσ g character Henning diffuse Rydberg series. The oscillator strengths of transitions between states involved in all possible resonant FWM processes are calculated, verifying that the nonlinear spectra are dominated by pathways described by an initial excitation to the diffuse nsσ g Rydberg series and emission from the sharp ndσ g Rydberg series. The results substantiate not only that attosecond XUV FWM spectroscopy produces rigorous and meaningful measurements of ultrafast dynamics in polyatomic systems, but also that nonlinear spectroscopic techniques are versatile tools to selectively probe dynamics that are otherwise difficult to access.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Hybrid Absorption–Crystallization Strategies for the Direct Air Capture of CO2 Using Phase-Changing Guanidium Bases: Insights from in Operando X-ray Scattering and Infrared Spectroscopy Measurements

Efforts to limit rising concentrations of CO 2 have motivated the development of negative emission technologies. Direct air capture (DAC) of CO 2 is one of the negative emissions technologies that has been proposed for the direct removal of CO 2 from the atmosphere. Phase-changing bis(iminonoguanidine) (BIG) sorbents have been developed for the direct air capture of CO 2 . These phase changing sorbents, specifically glyoxal-bis(iminoguanidine) (GBIG), involve (1) CO 2 absorption with aqueous amino acid salts, such as K- or Na-glycinate to yield bicarbonate-rich solutions, (2) crystallization of the bicarbonate anions with a BIG solid, which regenerates the amino acid, and (3) solid-state CO 2 release from the carbonate crystals and BIG regeneration. Despite the promising potential of these materials, their structural evolution during the thermal regeneration of the BIG solids, chemical regeneration of the sodium or potassium glycinate solvents, and the crystallization behavior of CO 2 -loaded BIG bicarbonate remain to be evaluated and understood in detail. The aim of this study is to probe these knowledge gaps. In situ wide-angle X-ray Scattering (WAXS) results show that CO 2 and water molecules in GBIG bicarbonate are simultaneously released in a single step during the thermal regeneration of the sorbent at 97 – 134 °C. In situ ATR-FTIR measurements showed that sodium glycinate and GBIG bicarbonate are simultaneously generated when GBIG, glycine, and sodium bicarbonate are reacted. The crystallization of GBIG bicarbonate from GBIG and CO 2 -loaded monoethanolamine (MEA) occurs rapidly in the first 10 min of the reaction, as determined using in situ GI-SAXS measurements. Overall, the insights from these studies are essential for the scalable implementation of CO 2 capture technologies using these phase-changing sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs 2 TeX 6 (X = Cl – , Br – , I – ) Single Crystals

The soft, dynamic lattice of inorganic lead halide perovskite CsPbX 3 (X = Cl ⁻ , Br ⁻ , I ⁻ ) leads to the emergence of many interesting photophysical and optoelectronic phenomena. However, probing their lattice dynamics with vibrational spectroscopy remains challenging. The influence of the fundamental octahedral building block in the perovskite lattice can be better resolved in zero-dimensional (0D) vacancy-ordered double perovskites of form A 2 BX 6 . Here we study Cs 2 TeX 6 (X = Cl ⁻ , Br ⁻ , I ⁻ ) single crystals to yield detailed insight into the fundamental octahedral building block and to explore the effect that its isolation in the crystal structure has on structural and electronic properties. The isolated [TeX 6 ] 2- octahedral units serve as the vibrational, absorbing, and emitting centers within the crystal. Serving as the vibrational centers, the isolated octahedra inform the likelihood of a random distribution of 10 octahedral symmetries within the mixed-halide spaces, as well as the presence of strong exciton-phonon coupling and anharmonic lattice dynamics. Serving as the absorbing and emitting centers, the isolated octahedra exhibit compositionally tunable absorption (1.50-3.15 eV) and emission (1.31-2.11 eV) energies. Due to greater molecular orbital overlap between neighboring octahedra with increasing halide anion size, there is a transition from a more molecule-like electronic structure in Cs 2 TeCl 6 and Cs 2 TeBr 6 -as expected from the effective 0D nature of these single crystals-to a dispersive electronic structure in Cs 2 TeI 6 , typical of three-dimensional (3D) bulk single crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1986

OH radical measurements by optical absorption spectroscopy

The long path absorption spectroscopy (LPA) measurement of OH utilizes the strong UV absorption spectrum of the molecule with well resolved rotational lines around 308 nm. The light source consists of an Ar ion laser pumped CW dye laser, the output of which is frequency doubled to emit a spectrally smooth light profile of 0.1 nm FWHM at 308 nm. This is considerably broader than the sharp (0.0018 nm wide) absorption features of OH and also wider than the total spectral region (0.06 nm) scanned around the OH lines. For field measurements a Cassegrain-type telescope expands the small diameter of the original laser beam by a factor of 50 to about a 0.25-m diameter in order to reduce the divergence of the beam as well as its mean photon flux density, thus reducing the maximum self-generated OH concentration to 40,000 cu. cm. The light is passed into the open atmosphere and reflected at about 5 km distance resulting in a 10-km light path length. A telescope focuses the returning light onto the entrance slit of a monochromator the single exit slit of which is replaced by a mechanical scanning device operating at a scan repetition rate of 6.6 KHz. For a typical measurement (1h duration) some 20,000,000 scans are averaged, rendering the contribution of atmospheric turbulence to the spectral noise negligible.

Platt, U.↗

DOE OSTI2021

Effect of Spin–Orbit Coupling on Phonon-Mediated Magnetic Relaxation in a Series of Zero-Valent Vanadium, Niobium, and Tantalum Isocyanide Complexes

Spin-vibronic coupling leads to spin relaxation in paramagnetic molecules, and an understanding of factors that contribute to this phenomenon is essential for designing next-generation spintronics technology, including single-molecule magnets and spin-based qubits, wherein long-lifetime magnetic ground states are desired. We report spectroscopic and magnetic characterization of the isoelectronic and isostructural series of homoleptic zerovalent transition metal triad M(CNDipp) 6 (M = V, Nb, Ta; CNDipp = 2,6-diisopropylphenyl isocyanide) and show experimentally the significant increase in spin relaxation rate upon going from V to Nb to Ta. Correlated electronic calculations and first principle spin–phonon computations support the role of spin–orbit coupling in modulating spin–phonon relaxation. Furthermore, our results provide experimental evidence that increasing magnetic anisotropy through spin–orbit coupling interactions leads to increased spin–vibronic relaxation, which is detrimental to long spin lifetime in paramagnetic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗