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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 1,513 records · Page 84
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Isolating the Contributions of Specific Network Sites to the Diffuse Vibrational Spectrum of Interfacial Water with Isotopomer-Selective Spectroscopy of Cold Clusters

Decoding the structural information contained in the interfacial vibrational spectrum of water requires understanding how the spectral signatures of individual water molecules respond to their local hydrogen bonding environments. In this study, we isolated the contributions for the five classes of sites that differ according to the number of donor (D) and acceptor (A) hydrogen bonds that characterize each site. These patterns were measured by exploiting the unique properties of the water cluster cage structures formed in the gas phase upon hydration of a series of cations M+·(H2O)n (M = Li, Na, Cs, NH4, CH3NH3, H3O, and n = 5, 20-22). This selection of ions was chosen to systematically express the A, AD, AAD, ADD, and AADD hydrogen bonding motifs. The spectral signatures of each site were measured using two-color, IR-IR isotopomer-selective photofragmentation vibrational spectroscopy of the cryogenically cooled, mass selected cluster ions in which a single intact H2O is introduced without isotopic scrambling, an important advantage afforded by the cluster regime. The resulting patterns provide an unprecedented picture of the intrinsic line shapes and spectral complexities associated with excitation of the individual OH groups, as well as the correlation between the frequencies of the two OH groups on the same water molecule, as a function of network site. The properties of the surrounding water network that govern this frequency map are evaluated by dissecting electronic structure calculations that explore how changes in the nearby network structures, both within and beyond the first hydration shell, affect the local frequency of an OH oscillator. The qualitative trends are recovered with a simple model that correlates the OH frequency with the network-modulated local electron density in the center of the OH bond.

Yang, Nan↗
DOE OSTI2020

Table-Top X-ray Spectroscopy of Benzene Radical Cation

Herein, ultrafast table-top X-ray spectroscopy at the carbon K-edge is used to measure the X-ray spectral features of benzene radical cations (Bz + ). The ground state of the cation is prepared selectively by two-photon ionization of neutral benzene, and the X-ray spectra are probed at early times after the ionization by transient absorption using X-rays produced by high harmonic generation (HHG). Bz + is well-known to undergo Jahn-Teller distortion, leading to a lower symmetry and splitting of the π orbitals. Comparison of the X-ray absorption spectra of the neutral and the cation reveals a splitting of the two degenerate π* orbitals as well as an appearance of a new peak due to excitation to the partially occupied π-subshell. The π* orbital splitting of the cation, elucidated on the basis of high-level calculations in a companion theoretical paper, is discovered to be due to both the symmetry distortion and even more dominant spin coupling of the unpaired electron in the partially vacant π orbital (from ionization) with the unpaired electrons resulting from the transition from the 1s C core orbital to the fully vacant π* orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Threshold Ionization Spectroscopy and Theoretical Calculations of LnO (Ln = La and Ce)

Mass-analyzed threshold ionization (MATI) spectroscopy was used to measure the vibronic spectra of LnO (Ln = La and Ce). Single-reference coupled cluster and relativistic multireference configuration calculations were carried out to compare with the measured vibronic energies. The spectrum of LaO displays a single vibronic band system, while that of CeO shows multiple ones. The ionization energies of LaO and CeO are measured as 5.2446 (6) and 5.3332(6) eV, respectively, which are a hundredfold improvement over the literature values. The vibrational energies of the neutral molecule and corresponding ion reveal the charge effect on the metal-oxygen bond of both species. The single band system in the spectrum of LaO arises from the transition of the ground state of the neutral molecule with the La(6s 1 )O(2p 6 ) valence configuration to the ground state of the singly charged ion with the La(6s o )O(2p 6 ) configuration. Here, the multiple band systems in the spectrum of CeO are attributed to the spin-orbit coupling for the Ce(4f 1 6s 1 )O(2p 6 ) configuration of the neutral molecule and an excited state for the Ce(4f 1 )O(2p 6 ) configuration of the ion.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Cryogenic Vibrationally Resolved Photoelectron Spectroscopy of OH–(H2O): Confirmation of Multidimensional Franck-Condon Simulation Results for the Transition State of the OH + H2O Reaction

We present a transition state spectroscopic study of the OH + H2O reaction using the experimental technique of cryogenic Negative Ion Photoelectron Spectroscopy (NIPES). The recorded NIPE spectrum at 193 nm exhibits multiple vibrational progressions that include excitations to the shared H atom antisymmetric stretching mode with an interval of 0.32 eV as well as other progressions, mainly involving the H bending and O…O symmetric stretching modes. The Vertical Detachment Energy (VDE) was measured at 3.53 eV, whereas an upper limit for the Adiabatic Detachment Energy (ADE) was estimated at 2.90 eV. These values are in excellent agreement with the theoretically computed values of 3.51 eV and 2.83 eV respectively, obtained at the CCSD(T)/aug-cc-pV5Z level of theory. The recorded NIPE spectrum is in very good agreement when compared to the one recently reported from four-dimensional Franck-Condon simulations, in which a similar spectral profile was predicted. Besides observing the ground state, a charge-transfer excited state in the form of [OH–(H2O)+] is identified with a relative energy of 1.39 eV, well matching the previous prediction of 1.36 eV. This work was supported by U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and performed using EMSL, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated by Battelle Memorial Institute for the DOE. The theoretical calculations were conducted on EMSL’s “Cascade” Supercomputer. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Cao, Wenjin↗
DOE OSTI2021

Photoelectron Spectroscopy and Theoretical Study on Monosolvated Cyanate Analogue Clusters ECX-· Sol (ECX- = NCSe-, AsCSe- and AsCS-; Sol = H2O, CH3CN)

Six monosolvated cyanate analogue clusters ECX-?Sol (ECX– = NCSe-, AsCSe-, and AsCS-; Sol = H2O and CH3CN) were investigated using negative ion photoelectron spectroscopy (NIPES). NIPES experiments show that these clusters possess overall similar spectra compared to their respective isolated ECX- anions but shift to higher electron binding energy with solvent CH3CN stabilizing the excess electrons slightly more than H2O. For the ECX-·H2O series, vertical detachment energies and their increments relative to the bare species are measured to be 3.700 / 0.370, 3.085 / 0.425, 3.085 / 0.430 eV for NCSe-, AsCSe- and AsCS-, respectively, while the corresponding values in ECX-·CH3CN series are 3.835 / 0.505, 3.145 / 0.475, and 3.135 / 0.480 eV. Ab initio electronic structure calculations indicate the excess charges located at the terminal N and Se atoms in NCSe- and migrated to the central C atom in AsCSe- and AsCS-. For NCSe-, the solvation is driven by the interactions with the two negatively charged terminal ends, while for AsCSe- and AsCS-, the solvation revolves around the interactions with the central C atom, where all the excess negative charge is concentrated. Two nearly degenerate isomers for NCSe-·H2O are identified, one forming a single strong N…H-O hydrogen bond (HB) and the other featuring a bidentate HB with two hydroxyl H atoms pointing to N and Se ends. In contrast, the negative central C atom in AsCSe-/AsCS- allows the formation of a bifurcated HB with H2O. Similar effects are observed for the acetonitrile case, in which the three H atoms of methyl group interact with the two negatively charged terminal ends in NCSe-, while prefer binding to the central negative carbon atom in AsCSe-/AsCS-. The different binding motifs derived in this work may suggest distinctly different solvation properties in NCSe- versus AsCSe-/AsCS-, with the former anion leading to asymmetric solvation at the N end of the solute, while the latter species creating more ‘isotropic’ solvation around the central C equatorial plane. This work was supported by U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and performed using EMSL, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated by Battelle Memorial Institute for the DOE. The theoretical calculations were conducted on EMSL’s “Cascade” Supercomputer.

Yuan, Qinqin↗
DOE OSTI2022

Substituent Effects on the Electronic Spectroscopy of Four-Carbon Criegee Intermediates

Atmospheric ozonolysis of biogenic and anthropogenic alkenes generates zwitterionic carbonyl oxide intermediates (R 1 R 2 C=O + O – ), known as Criegee intermediates, with different structural motifs and conformations. This study reports a systematic laboratory study of substituent effects on the electronic spectroscopy of four-carbon Criegee intermediates (CIs) with methyl–ethyl (MECI) and isopropyl (IPCI) groups, which are isomers produced in ozonolysis of asymmetric branched alkenes. The four-carbon CIs are separately generated by an alternative synthetic route, and spectroscopically characterized on the strong π* ← π transition associated with the carbonyl oxide group in a pulsed supersonic expansion with VUV photoionization at 118 nm and UV-induced depletion of the m/z 88 signal. The resultant broad and unstructured UV spectral features for MECI and IPCI are peaked at ca. 320 and 330 nm, respectively, with large absorption cross-sections of ca. 10 –17 cm 2 . Comparisons are made with the four-carbon CIs formed in isoprene ozonolysis, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide), which have the same backbone connectivity as MECI and IPCI but have extended conjugation across the vinyl and carbonyl groups. A remarkable 50 nm shift of the peak absorption to longer wavelength is observed for MVK-oxide and MACR-oxide compared to MECI and IPCI, respectively. Furthermore, vertical excitation energies computed theoretically agree well with the experimental findings, confirming that the spectral shifts are caused by the extended π conjugation in the isoprene-derived Criegee intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electronic Properties of UN and UN – from Photoelectron Spectroscopy and Correlated Molecular Orbital Theory

In this work, the results of calculations of the properties of the anion UN – including electron detachment are described, which further expand our knowledge of this diatomic molecule. High-level electronic structure calculations were conducted for the UN and UN – diatomic molecules and compared to photoelectron spectroscopy measurements. The low-lying Ω states were obtained using multireference CASPT2 including spin-orbit effects up to ~20,000 cm –1 . At the Feller–Peterson–Dixon (FPD) level, the adiabatic electron affinity (AEA) of UN is estimated to be 1.402 eV and the vertical detachment energy (VDE) is 1.423 eV. The assignment of the UN excited states shows good agreement with the experimental results with a VDE of 1.424 eV. An Ω = 4 ground state was obtained for UN – which is mainly associated with the 3 H ΛS state. Thermochemical calculations estimate a bond dissociation energy (BDE) for UN – (U – + N) of 665.9 kJ/mol, ~15% larger than that of UN and UN + . The NBO analysis reveals U–N triple bonds for the UN, UN – , and UN + species.

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

Ultrafast X-ray Spectroscopy of Intersystem Crossing in Hexafluoroacetylacetone: Chromophore Photophysics and Spectral Changes in the Face of Electron-Withdrawing Groups

Intersystem crossings between singlet and triplet states represent a crucial relaxation pathway in photochemical processes. Herein, we probe the intersystem crossing in hexafluoro-acetylacetone with ultrafast X-ray transient absorption spectroscopy at the carbon K-edge. In this study, we observe the excited state dynamics following excitation with 266 nm UV light to the 1 ππ* (S 2 ) state with element and site-specificity using a broadband soft X-ray pulse produced by high harmonic generation. These results are compared to X-ray spectra computed from orbital optimized density functional theory methods. It is found that the electron-withdrawing fluorine atoms decongest the X-ray absorption spectrum by enhancing separation between features originating from different carbon atoms. This facilitates the elucidation of structural and electronic dynamics at the chromophore. The evolution of the core-to-valence resonances at the carbon K-edge reveals an ultrafast population transfer between the 1 nπ* (S 1 ) and 3 ππ* (T 1 ) states on a 1.6 ± 0.4 ps time scale, which is similar to the 1.5 ps time scale earlier observed for acetylacetone [ J. Am. Chem. Soc. 2017, 139, 16576—16583, DOI: 10.1021/jacs.7b07532]. It therefore appears that terminal fluorination has little influence on the intersystem crossing rate of the acetylacetone chromophore. In addition, the significant role of hydrogen-bond opened and twisted rotational isomers is elucidated in the excited state dynamics by comparison of the experimental transient X-ray spectra with theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Photoelectron Spectroscopy and Computational Study on Microsolvated [B 10 H 10 ] 2– Clusters and Comparisons to Their [B 12 H 12 ] 2– Analogues

Microhydrated closo-Boranes have attracted great interests due to their superchaotropic activity related to well-known Hofmeister effect and important applications in biomedical and battery fields. In this work, we report a combined negative ion photoelectron spectroscopy and quantum chemical investigation on hydrated closo-decaborate clusters [B 10 H 10 ] 2- ·nH 2 O (n = 1 – 7) with a direct comparison to their analogues [B 12 H 12 ] 2- ·nH 2 O and free water clusters. A single H 2 O molecule is found sufficient to stabilize the intrinsically unstable [B 10 H 10 ] 2- dianion. The first two water molecules strongly interact with the solute forming B-H···H-O dihydrogen bonds while additional water molecules show substantially reduced binding energies. Unlike [B 12 H 12 ] 2- ·nH 2 O possessing highly structured water network with the attached H 2 O molecules arranged in a unified pattern by maximizing B-H···H-O dihydrogen bonding, distinct structural arrangements of the water clusters within [B 10 H 10 ] 2– ·nH 2 O are achieved with the water cluster networks from trimer to heptamer resembling free water clusters. Such a distinct difference arises from the variations in size, symmetry, and charge distributions between these two dianions. Finally, the present finding again confirms the structural diversity of hydrogen-bonding networks in microhydrated closo-boranes and enrich our understanding of aqueous borate chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Activation, Dehydrogenation, and Carbon–Carbon Coupling of Methane by Iridium Cations Studied by Infrared Multiple Photon Dissociation Spectroscopy and Density Functional Theory

Products resulting from the sequential activation of one, two, three, and four methane molecules by atomic iridium cations were characterized by gas-phase infrared multiple photon dissociation spectroscopy and density functional theory (DFT) calculations. Iridium cations were generated using a laser ablation source and reacted with methane in a linear radiofrequency ion trap before mass analysis and spectroscopic interrogation in a Fourier transform ion cyclotron resonance mass spectrometer coupled to the free-electron laser for intracavity experiments (FELICE) beamline. Product ions were irradiated using infrared light over the 250–1500 cm –1 range. Comparisons between the experimental and DFT-calculated spectra enabled structural determination of the products formed. The observed products include HIrCH + , Ir(CH 2 ) 2 + , H s Ir(C 3 H 5 ) + , and Ir(CH 3 ) s (C 3 H 5 ) + , where the subscript s denotes a syn orientation of the two ligands. Furthermore, formation of the latter two products provides evidence for efficient C–H bond activation and subsequent C–C coupling on the atomic iridium cation.

Chemical reactions↗
DOE OSTI2025

From Electronic Structure to Ion Transport: Photoelectron Spectroscopy and Molecular Dynamics Simulations Reveal the Role of Anions in Lithium Battery Electrolytes

Electrolyte anions are pivotal for lithium battery performance, yet their fundamental electronic structural properties are not well understood. In this work, we employ a combination of negative-ion photoelectron spectroscopy (NIPES), ab initio calculations, and molecular dynamics (MD) simulations to investigate the electronic structures of three representative electrolyte anions. This multiscale approach enables us to elucidate how their intrinsic electronic properties govern anion–solvent interactions in gas-phase clusters, as well as lithium-ion (Li + ) solvation structures and ion transport behavior in the condensed phase. NIPES reveals that difluoro(oxalato)borate (DFOB – ), bis(fluorosulfonyl)imide (FSI – ), and bis(oxalato)borate (BOB – ) all exhibit high electron binding energies, with vertical/adiabatic detachment energies increasing from DFOB – (6.09/5.70 eV) to FSI – (6.80/6.10 eV) to BOB – (6.82/6.40 eV), correlating with enhanced oxidation stability. Ab initio calculations reveal that DFOB – /FSI – –solvent complexes bind Li + ∼ 10 kcal/mol stronger than BOB – series, aligning with the strength of a Li + –anion model. DFOB – exhibits pronounced charge localization on both oxygen and fluorine atoms, enabling their involvement in Li + coordination. In contrast, fluorine atoms in FSI – are largely electron-depleted and remain excluded from direct Li + binding. MD simulations further demonstrate that LiDFOB and LiFSI systems exhibit Li + diffusion coefficients three and five times higher than those of LiBOB across four common solvents. Notably, LiFSI salt in acetonitrile (AN) exhibits the fastest Li + diffusion among 12 electrolyte systems, highlighting the synergistic effect of FSI – and AN in promoting ion mobility. In conclusion, these findings provide a molecular-level understanding of the critical roles of anion and its microsolvation in optimizing Li + diffusion dynamics, once again emphasizing the positioning of FSI – and DFOB – as prime candidates for next-generation electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2026

Uranium Hexafluoride Hydrolysis Reaction Dynamics from Cryogenic Layering, FTIR Spectroscopy, and Isotopic Substitution

The first direct evidence that the hydrolysis reaction of uranium hexafluoride (UF 6 ) follows multiple competing pathways which are driven by the ratio of water to UF 6 , temperature, and isotopic composition is presented. Using temperature dependent infrared spectroscopy, it is shown the hydrolysis can be prevented at temperatures below 150 K, and that water-rich environments promote the formation of uranium oxyfluoride intermediates. Spectral shifts reveal isomeric transitions and the growth of polymeric species, with reaction reversibility observed at high water concentrations. Additionally, controlled heating rates affect the emergence of intermediates. The final particulate product consistently forms as uranyl fluoride hydrate, though its morphology and spectral signature vary with reaction conditions and annealing. These findings help clarify long-standing uncertainties surrounding UF 6 hydrolysis.

Chemical reactions↗
DOE OSTI2026

Fingerprinting Uranium Oxides with Electron Energy Loss Spectroscopy Supported by Theoretical Computations

Uranium oxides occur in a variety of phases that differ in crystal structure and uranium oxidation states. Electron energy loss spectroscopy (EELS) is one of the few techniques that has sufficient spatial resolution and sensitivity to electronic structure to distinguish amongst phases at the nanoscale. However, beam-sensitive materials such as uranium oxides are subject to spectral modification due to interactions with the electron beam. Therefore, theory support is essential to reliably exclude the impact of beam damage and generate true reference datasets. Here we use a comparison of theoretical and experimental spectra to probe the impact of beam damage on O K-edge and U N-edge (N6,7 and N4,5) EELS spectra of various single-valent and mixed-valence uranium oxide bulk phases. Using a low-dose experimental set-up, we show that the O K-edge theoretical spectra are in excellent agreement with experiment for both peak positions and relative intensities of respective peaks. In contrast, U N-edge features are less distinguishing due to the partially localized nature of the U 5f orbitals and overlapping multiplet and spin–orbit coupling effects. This work demonstrates that O K-edge EELS is sufficiently diagnostic to distinguish a wide range of uranium oxides and that the experimental approach used here minimizes beam damage and allows valence state discrimination across the U(IV), U(V) and U(VI) series. When combined with imaging modes available in electron mi-croscopy, the work enables detailed investigation and characterization of uranium redox transformations at the nanoscale.

Carbone, Jacopo↗
DOE OSTI2026

New Perspectives on Vibrational Energy Transfer in Energetic Materials: Insights from Pressure-Tuned Ultrafast Spectroscopy

Understanding the manner in which vibrational energy flows between molecular and lattice vibrations is of great interest in physical chemistry due to its central role in reactivity and energy dissipation in molecular materials. Here, in this feature article, we highlight our recent efforts employing ultrafast broadband infrared spectroscopy toward understanding the interplay between molecular and lattice vibrations in energetic materials, motivated by the open questions surrounding the role of vibrational energy transfer (VET) in reaction initiation in these materials. Our work addresses the ongoing debate on the participation of doorway modes in VET. We further present new results from high-pressure ultrafast experiments on RDX, a hydrogen-bonded material, and BNFF, a hydrogen-free material, to explore how intermolecular interaction strength governs VET pathways and time scales. Collectively, our findings reveal that vibrational dynamics in these systems occurs across three distinct time regimes, with VET being incomplete out to hundreds of picoseconds, suggesting the importance of considering nonstatistical reactions in the modeling of these materials. These time scales vary as intermolecular interaction strength is indirectly modified by application of static pressure, indicating dramatic changes to the vibrational structure of these materials under shock-relevant conditions. Our results thus shed light on how intermolecular interactions shape vibrational energy redistribution in molecular materials, and highlight the need for further theoretical and experimental investigation.

Carlson, Daniel Ryan [Sandia National Laboratories↗
DOE OSTI2019

Moisture Corrosion of LiH: A Kinetic Investigation by DRIFT Spectroscopy

Lithium hydride (LiH) is a unique, ionic compound with applications in a variety of industries. Unfortunately, LiH is very reactive toward H 2 O even at ppm levels, forming oxide (Li 2 O) and hydroxide (LiOH) corrosion layers while outgassing H 2 . An effective means to eliminate unwanted outgassing is vacuum-heating to convert LiOH into Li 2 O, although subsequent re-exposure to moisture during transport/handling reconverts some Li 2 O back to LiOH. A corrosion growth model for previously vacuum-baked LiH is necessary for long-term prediction of the hydrolysis of LiH. In this work, a para-linear hydroxide corrosion growth model is proposed for the reaction of previously vacuum-baked LiH samples with moisture. This model, composed of two competing diffusion reaction fronts at the LiOH/Li 2 O and Li 2 O/LiH interfaces, is validated experimentally by subjecting a previously vacuum-baked polycrystalline LiH sample to 35 ppm of H 2 O at room temperature while monitoring the corrosion growth as a function of time with diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy. The para-linear growth model for the hydrolysis of previously vacuum-baked LiH proposed in this report can also serve as a template for the hydrolysis of other hygroscopic oxides grown on metal or metal hydride substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Tuning the Cation–Anion Interactions by Methylation of the Pyridinium Cation: An X-ray Photoelectron Spectroscopy Study of Picolinium Ionic Liquids

Here, X-ray photoelectron spectroscopy is used to investigate the impact of methylation on the electronic environment of pyridinium cations. Because of the electron-donating effect of the methyl group, there is a significant increase in electron density on the cationic nitrogen. The shift of the N 1s binding energy is inversely proportional to the anion basicity. The methylation position on the electronic environment of the cationic nitrogen is investigated. The N 1s binding energy follows the trend: 1-octylpyridinium > 1-octyl-3-picolinium > 1-octyl-4-picolinium > 1-octyl-2-picolinium, which is in good agreement with the cation acidity. The increase in the inductive effect subsequently weakens the cation–anion interactions through charge transfer from the anion to the cation, causing a subtle change in the electronic environment of the anion. Such an effect is noticeably reflected in the Br 3d binding energy. It shows that the Br 3d 5/2 binding energy of 1-octyl-2-picolinium bromide is 0.2 eV lower than that of 1-octylpyridinium bromide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Unraveling Local Structure of Molten Salts via X-ray Scattering, Raman Spectroscopy, and Ab Initio Molecular Dynamics

In this work, we resolve a long-standing issue concerning the local structure of molten MgCl 2 by employing a multimodal approach, including X-ray scattering and Raman spectroscopy, along with the theoretical modeling of the experimental spectra based on ab initio molecular dynamics (AIMD) simulations utilizing several density functional theory (DFT) methods. We demonstrate the reliability of AIMD simulations in achieving excellent agreement between the experimental and simulated spectra for MgCl 2 and 50 mol % MgCl 2 + 50 mol % KCl, and ZnCl 2 , thus allowing structural insights not directly available from experiment alone. A thorough computational analysis using five DFT methods provides a convergent view that octahedrally coordinated magnesium in pure MgCl 2 upon melting preferentially coordinates with five chloride anions to form distorted square pyramidal polyhedra that are connected via corners and to a lesser degree via edges. This is contrasted with the results for ZnCl 2 , which does not change its tetrahedral coordination on melting. Although the five-coordinate MgCl 5 3– complex was not considered in the early literature, together with an increasing tendency to form a tetrahedrally coordinated complex with decreasing the MgCl 2 content in the mixture with alkali metal chloride systems, current work reconciles the results of most previous seemingly contradictory experimental studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Observation of Collective Molecular Dynamics in a Chalcogenide Glass: Results from X-ray Photon Correlation Spectroscopy

The structural relaxation processes in a Ge 3 As 52 S 45 molecular chalcogenide glass sample were directly studied by X-ray photon correlation spectroscopy (XPCS). XPCS was conducted at the first sharp diffraction peak at q = 1.16 Å -1 at temperatures ranging from 123 K to above the glass transition at 328 K, and the results showed two different dynamical regimes. At a low temperature, the observed glass dynamics are slow and dominated by X-ray-photon-induced effects, which are temperature independent. At a higher temperature, we observed a dramatic decrease in the fluctuation timescales, indicating that the dynamics were mainly due to the intermolecular correlation of the As 4 S 3 molecule in the glass. The timescales in this high-temperature range agree well with those determined from measurements of the Newtonian viscosity. Here our XPCS studies suggest an extended length scale of the relaxation process in glassy Ge 3 As 52 S 45 from the single molecule to the intermolecular range across the glass transition, providing a unique direct probe of the dynamics beyond the length scales of the individual molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗