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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

An unwanted guest in the electrochemical oxidation of high-voltage Li-ion battery electrolytes: the life of highly reactive protons

Lithium-ion batteries (LIBs) are central to the urgent societal need to decarbonize both transportation and energy storage on the grid. Unfortunately, despite their attractive energy/power density, as well as high coulombic and energy efficiencies, further improvement of this technology – especially their durability – is desperately needed. To support these efforts, our study focuses on fundamental understanding of the decomposition pathways for LIB electrolytes at the cathode–electrolyte interface (CEI), as the nature of these reactions directly controls the extent to which cell capacity and voltage decays in these systems. In this study, we employ electrochemical methods, coupled with product analysis using NMR spectroscopy and mass spectrometry, to determine the decomposition mechanisms in both model and technologically relevant electrolytes. Remarkably, we discovered the electrochemical formation of protons with high chemical activity, comparable to known superacids, at potentials relevant to practical Li-ion batteries. Their reactivity toward every individual component of the CEI provides a unified thermochemical origin for a myriad of side reactions that are commonly associated with the electrochemical reaction. In particular, electrochemically generated protons react with intact EC molecules to form CO 2 and other short and long chain ethers. They also undergo an acid–base reaction with LiPF 6 , to form the weaker acid HF, and with the cathode active material, leaching transition metals into the electrolyte. Collectively, the results of this study all point to the urgent need to either mitigate this proton formation or introduce benign harvesting additives via new electrolyte design strategies.

Ilic, Stefan [Argonne National Laboratory (ANL), A↗
DOE OSTI2026

Gold Quantum Rods: Modulation of Singlet and Triplet Exciton Populations by the Rod Length

Abstract Gold quantum rods (QRs) of Au60, Au78, Au96, and Au114 (protected by thiolate ligands) exhibit exclusive fluorescence, which is different from the shorter Au42 QR with dual emission (fluorescence + phosphorescence). Herein, we report the excitation wavelength-dependent near-infrared-II photoluminescence (PL) and exciton dynamics of this series of QRs. Interestingly, the fluorescence quantum yield (QY) of the QRs is much higher (2–10×) when the lowest singlet excited state (S1) is excited compared to the excitation of high-lying states (Sn). A metastable intermediate singlet state (denoted S′) is identified by transient absorption spectroscopy when Sn is excited, and this S′ state leads to fast “skybridge” intersystem crossing (ISC), which contributes primarily (>60%) to the total triplet population. With increasing aspect ratio (AR) of QRs (from 6.3 to 18.7), nonradiative processes accelerate, leading to fast decay of the S1 state (hence, less QY) and of the T1 state (barely phosphorescent). A detailed energy flow mechanism is determined for the QRs after photoexcitation, which offers a design principle for manipulation of exciton dynamics toward potential utilization of higher excited states in applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS1972

Research on the properties and interactions of simple atomic and ionic systems

Simple ionic systems were studied, such as metastable autoionizing states of the negative He ion, two-photon decay spectrum of metastable He ion, optical excitation with low energy ions, and lifetime measurements of singly ionized Li and metastable He ion. Simple atomic systems were also investigated. Metastable autoionizing atomic energy levels in alkali elements were included, along with lifetime measurements of Cr-53, group 2A isotopes, and alkali metal atoms using level crossing and optical double resonance spectroscopy.

Novick, R.↗
DOE OSTI2022

Identification of excited states in Bi 188 and Po 188

The neutron-deficient 188 Bi and 188 Po isotopes have been studied by γ-ray spectroscopy using the recoil-decay tagging technique with the Argonne Gas-Filled Analyzer. A new 0.25(5)-μs isomeric state and a prompt cascade formed by 319-, 366-, and 462-keV γ rays have been established on top of the (10¯) α -decaying isomer in 188 Bi. The first excited (2 + ) state in 188 Po was identified, its excitation energy of 242(2) keV continues the nearly constant trend for the first 2 + states in 190, 192,194 Po. Here, the state is most likely a member of a prolate rotational band built on the ground state, albeit mixing with other coexisting configurations cannot be excluded. The new results obtained in the present work provide new information to shape coexistence in bismuth and polonium isotopes near the neutron midshell at N = 104 . In this mass region, a reduction in the prompt γ-ray yield obtained with recoil decay tagging was observed for a few nuclides, and the possible reasons are presented.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Crosslinked Polyethyleneimine Gel Polymer Interface to Improve Cycling Stability of RFBs

Redox flow batteries are considered a promising technology for grid energy storage. However, capacity decay caused by crossover of active materials is a universal challenge for many flow battery systems, which are based on various chemistries. In this paper, using the vanadium redox flow battery as an example, we demonstrate a new gel polymer interface (GPI) consisting of crosslinked polyethyleneimine with a large amount of amino and carboxylic acid groups introduced between the positive electrode and the membrane. The GPI functions as a key component to prevent vanadium ions from crossing the membrane, thus supporting stable long-term cycling. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted to investigate the effect of GPI on the electrochemical properties of graphitic carbon electrodes (GCFs) and redox reaction of catholyte. X-ray photoelectron spectroscopy (XPS) and 1 H nuclear magnetic resonance (NMR) spectra demonstrated that the crosslinked GPI is chemically stable for 100 cycles without dissolution of polymers and swelling in the strong acidic electrolytes. Results from inductively coupled plasma mass spectrometry (ICP-MS), Fourier-transform infrared (FTIR) spectroscopy, and energy-dispersive X-ray (EDX) spectroscopy proved that the GPI is effective in maintaining the concentration of vanadium species in their respective half-cells, resulting in improved cycling stability because of it prevents active species from crossing the membrane and stabilizes the oxidation states of active species.

Lim, Hyung-Seok↗
DOE OSTI2020

Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems

Lead sulfide (PbS) quantum dots (QDs) have shown promising performance as a sensitizer in infrared-to-visible photon upconversion systems. To investigate the key design rules, we compare three PbS-sensitized upconversion systems using three mediator molecules with the same tetracene triplet acceptor at different distances from the QD. Using transient absorption spectroscopy, we directly measure the triplet energy-transfer rates and efficiencies from the QD to the mediator and from the mediator to the emitter. With increasing distance between the mediator and PbS QD, the efficiency of the first triplet energy transfer from the QD to the mediator decreases because of a decrease in the rate of this triplet energy-transfer step, while the efficiency of the second triplet energy transfer from the mediator to the emitter increases because of a reduction in the QD-induced mediator triplet state decay. The latter effect is a result of the slow rate constant of the second triplet energy-transfer process, which is 3 orders of magnitude slower than the diffusion-limited value. The combined results lead to a net decrease of the steady-state upconversion quantum yield with distance, which could be predicted by our kinetic model. Our result shows that the QD/mediator interface affects both the first and second triplet energy transfer processes in the photon upconversion system, and the QD/mediator distance has an opposite effect on the efficiencies of the first and second triplet energy transfer. Lastly, these findings provide important insight for the further rational improvement of the overall efficiency of QD-based upconversion systems.

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

Charge Transfer and Recombination Pathways through Fullerene Guests in Porphyrin-Based MOFs

Porphyrin-based metal–organic frameworks (MOFs) offer a unique platform for building porous donor–acceptor networks that exhibit long-lived charge separation and transport upon incorporation of electron acceptor guest species. Here, in this work, porphyrin-based MOFs, PCN-222(H 2 ) and PCN-222(Zn), synthesized as nanoparticle suspensions, are successfully infiltrated with fullerene acceptor molecules, C 60 or PC 61 BM, in both polar and nonpolar solvent environments. The location and relative binding strength of these guest species are evaluated through a combination of N 2 physisorption measurements, photoluminescence quenching, and UV–vis absorption titration experiments. Semiempirical tight binding calculations are used to screen potential locations of the fullerene guest within the MOF pores, and hybrid density functional theory (DFT)-computed interaction energies confirm the energetically favorable positions. The fundamental photophysics of these donor–acceptor host–guest combinations are probed using ultrafast transient absorption spectroscopy. Sub-picosecond electron transfer involving initial exciplex population is observed, with slow charge recombination lifetimes on the order of τ ~1 ns for all systems in both dimethylformamide and 1,4-dioxane. Charge recombination occurs through population of fullerene and/or framework porphyrin triplet states depending on the porphyrin metalation status. The photophysics of the fullerene-loaded MOFs are discussed in the context of relevant porphyrin–fullerene donor–acceptor molecules to highlight the unique role of the framework environment in dictating photoinduced electron transfer and decay pathways.

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

Experimental study of atmospheric pressure single-pulse nanosecond discharge in pin-to-pin configuration

We present an experimental study of nanosecond high-voltage discharges in a pin-to-pin electrode configuration at atmospheric conditions operating in single-pulse mode (no memory effects). Discharge parameters were measured using microwave Rayleigh scattering, laser Rayleigh scattering, optical emission spectroscopy enhanced with a nanosecond probing pulse, and fast photography. Spark and corona discharge regimes were studied for electrode gap sizes 2-10 mm and discharge pulse duration of 90 ns. The spark regime was observed for gaps < 6 mm using discharge pulse energies of 0.6-1 mJ per mm of the gap length. Higher electron number densities, total electron number per gap length, discharge currents, and gas temperatures were observed for smaller electrode gaps and larger pulse energies, reaching maximal values of about 7.5 x 10 15 cm -3 , 3.5 x 10 11 electrons per mm, 22 A, and 4,000 K (at 10 microseconds after the discharge), respectively, for a 2 mm gap and 1 mJ/mm discharge pulse energy. Initial breakdown was followed by a secondary breakdown occurring about 30-70 ns later and was associated with ignition of a cathode spot and transition to cathodic arc. Here, a majority of the discharge pulse energy was deposited into the gas before the secondary breakdown (85-89%). The electron number density after the ns-discharge pulse decayed with a characteristic time scale of 150 ns governed by dissociative recombination and electron attachment to oxygen mechanisms. For the corona regime, substantially lower pulse energies (~0.1 mJ/mm), peak conduction current (1-2 A), and electron numbers (3-5 x 10 10 electrons per mm), and gas temperatures (360 K) were observed.

42 ENGINEERING↗
DOE OSTI2022

Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates

Molecular aggregates are of interest to a broad range of fields including light harvesting, organic optoelectronics, and nanoscale computing. In molecular aggregates, nonradiative decay pathways may emerge that were not present in the constituent molecules. Such nonradiative decay pathways may include singlet fission, excimer relaxation, and symmetry-breaking charge transfer. Singlet fission, sometimes referred to as excitation multiplication, is of great interest to the fields of energy conversion and quantum information. For example, endothermic singlet fission, which avoids energy loss, has been observed in covalently bound, linear perylene trimers and tetramers. In this work, the electronic structure and excited-state dynamics of dimers of a perylene derivative templated using DNA were investigated. Specifically, DNA Holliday junctions were used to template the aggregation of two perylene molecules covalently linked to a modified uracil nucleobase through an ethynyl group. The perylenes were templated in the form of monomer, transverse dimer, and adjacent dimer configurations. The electronic structure of the perylene monomers and dimers were characterized via steady-state absorption and fluorescence spectroscopy. Initial insights into their excited-state dynamics were gleaned from relative fluorescence intensity measurements, which indicated that a new nonradiative decay pathway emerges in the dimers. Femtosecond visible transient absorption spectroscopy was subsequently used to elucidate the excited-state dynamics. A new excited-state absorption feature grows in on the tens of picosecond timescale in the dimers, which is attributed to the formation of perylene anions and cations resulting from symmetry-breaking charge transfer. Given the close proximity required for symmetry-breaking charge transfer, the results shed promising light on the prospect of singlet fission in DNA-templated molecular aggregates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Illuminating the Photophysics of Oxygen Atom Transfer in Rare Earth Metal-Organic Complexes

Industrial separations of rare earth metals are reliant on selectivity based on ionic radii, which are time, energy, and resource consuming.1 The unique and discontinuous manifold of energy states associated with the f-electron configurations of the rare earth ions2 offer an opportunity to overcome some of these limitations by incorporating light into the separation process. Here, we use transient absorption spectroscopy to understand the differences in mechanism of light-initiated oxygen atom transfer (OAT) in yttrium (Y) and dysprosium (Dy) rare earth complexes. These metal-organic complexes are functionalized with hexfluoroacetyl-acetonate (hfac) and 4-methylmorpholine-N-oxide (NMMO). After light absorption in the presence of triphenyl phosphine (TPP), the NMMO in the Y-NMMO complex is replaced by the TPPO OAT reaction product. Because the Dy f-electron manifold is accessible to the ligand excited states, while there are no accessible states associated with f-electrons for Y, there are significant differences in reactivity. Transient absorption spectroscopy (TAS) was used to monitor changes after 340 nm photoexcitation of Dy/Y-NMMO or the product complex Dy/Y-TPPO. TAS is a pump-probe technique where a white light probe pulse is delayed relative to a visible pump pulse, which photoexcites a sample. Differences between the ground and excited states are monitored over time. With TAS, we access time scales from 100 fs-400 us to determine the photophysics of the complexes of interest. Photoexcitation of Y-NMMO (Fig. 1A) creates a broad photoinduced absorption (PIA) that evolves into a sharp positive feature over 4.2 ps centered at 450 nm. A secondary feature centered at 550 nm grows in with a 200 ps time constant and remains through the 5 ns time window of our experiment. Control experiments for Y-TPPO reveal that the feature at 450 nm is due to internal dynamics of the hfac ligand, while the 550 nm shoulder is due to the presence of the NMMO. Comparing kinetics at 550 nm for Y-NMMO and Dy-NMMO (Fig. 1B) shows that while Y exhibits a distinct growth in the NMMO feature, the Dy decays almost completely within 5 ns. Control experiments with Dy-TPPO prove that the ligand excited states centered on the hfac ligand are deactivated via energy transfer to the Dy manifold within 200 ps. This deactivation leads to significant differences in OAT reactivity between Y and Dy.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS↗
DOE OSTI2024

Proton diffusion and hydrogen/deuterium exchange in amorphous solid water at temperatures from 114 to 134 K

The reaction coefficient for hydrogen/deuterium (H/D) exchange and the diffusion of hydrated excess protons within amorphous solid water (ASW) are characterized as a function of temperature. For these experiments, water films are deposited on a Pt(111) substrate at 108 K, and reactions with pre-adsorbed hydrogen atoms produce hydrated protons. Upon heating, protons diffuse within the water, and H/D exchange occurs when they encounter D2O probe molecules deposited in the films. The time-dependent concentration of D2O is monitored with infrared spectroscopy, and it indicates the protons diffusion from the substrate and establish an equilibrium distribution prior to significant H/D exchange for temperatures 114 K ≤T≤ 134 K. By controlling the distance between the D2O molecules and the substrate, we probe the distribution of protons within the film. It decays as x−2 for the examined range of x (12–52 nm) due to the electric field that develops between the diffusing protons and their image charges in the metal substrate. This agrees with the theoretical distance scaling for the equilibrated proton concentration in a dielectric near a metal boundary. From the proton concentration and the measured D2O decay rate, a lower bound for the proton diffusion coefficient ranging from 10−20 m2/s at 114 K to 10−18 m2/s at 134 K is estimated. The diffusion coefficient has an activation energy of 0.40 eV, which is comparable to energies reported for molecular translations and rotations of H2O, suggesting they may play a critical role in the proton diffusion mechanism within ASW.

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

Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials

We see that cation-disordered Li-excess cathodes with oxygen redox reactions are promising candidates for high-energy-density Li ion batteries. Nevertheless, the oxygen redox process that is required for the high capacity often comes with the oxygen loss, which leads to severe capacity degradation and voltage decay. In this work, we have successfully synthesized a series of Li-excess cation-disordered cathodes (Li 1.2 Mn 0.4+x Ti 0.4-x O 2-x Fx) (0 ≤ x ≤ 0.2) with different fluorine (F) contents. The electrochemical performance results show that the Li 1.2 Mn 0.55 Ti 0.25 O 1.85 F 0.15 (LMTOF0.15) exhibits the highest reversible capacity (275 mAh g -1 , under 30 mA g -1 ), cyclability, and voltage retentions. The mapping of resonant inelastic X-ray scattering (mRIXS) and differential electrochemical mass spectroscopy (DEMS) results reveal that the fluorination enhances the reversible lattice oxygen redox reaction while suppressing irreversible gas release and surface reactions. The X-ray Absorption Spectroscopy (XAS) during the initial two cycles shows that F-substitution alleviates the reduction of the Mn valence state during the whole (dis)charge processes in the bulk and at the surface of the material, results in higher average discharge voltage. In addition, the introduction of F improves the structural stability and suppresses local lattice distortion of the material. Therefore, LMTOF 0.15 is able to cycle with smaller polarization, less interfacial side reaction and Mn dissolution, and therefore results in enhanced cyclability. This work provides a comprehensive understanding of the fluorination effect on the cationic and anionic redox activities in cation-disordered Li-excess cathodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Studies of surface adsorbate electronic structure and femtochemistry at the fundamental length and time scales. Final report

The electronic structure and ultrafast (10-15 s-femtosecond timescale) electron dynamics were investigated for clean and atom/molecule covered metal surfaces. The studies were performed by scanning tunneling microscopy (STM) to measure the structure of adsorbed atoms and molecules on metal surfaces, and to investigate their electronic properties. The electronic structure of the observed molecular networks was calculated by electronic structure theory in collaboration with Prof. Jin Zhao, who is a long-time collaborator, a Professor at the University of Science and Technology of China, and holds an Adjunct Professorship at the University of Pittsburgh. We also investigated the electronic properties of C60 molecules when they are templated by corrugated black phosphorous surfaces. We found unexpected charge delocalization that is enabled by the templating. This research was done in collaboration with Professor Min Feng at the Wuhan University, and who also holds an Adjunct Professorship at the University of Pittsburgh. Moreover, the electronic structure and electron dynamics in metal surfaces were investigated by time-resolved photoemission electron spectroscopy. The focus of ultrafast spectroscopy has been on the plasmonic response of silver surfaces. One direction has been to develop multidimensional (energy, momentum, and time) photoelectron spectroscopy of the coherent response of solid surfaces. This method was applied to study the collective electron excitations known generally as plasmons, which screen optical fields from penetration into metals. Although this collective response has been known for more than 60 years and is used extensively to deposit optical energy into metals, how this happens is poorly known. We investigated the plasmonic response of silver at the point where the dielectric response passes through zero and bulk plasmon is excited by light. We discovered that the plasmon excitation decays by exciting electrons from the Fermi level of a metal, which is contrary to what is believed in the plasmonic science community. This research has been performed in collaboration with Dr. Marcel Reutzel, who was a postdoctoral fellow working on this research at the University of Pittsburgh, and now has a faculty position at the University of Göttingen in Germany. Prof. Branko Gumhalter from the Institute of Physics in Zagreb contributed on the theory of plasmonic decay processes. Furthermore, we investigated the Floquet engineering of electronic bands in metals leading to multiphoton photoemission and above threshold photoemission. Finally, we demonstrated that it is possible to change the electronic structure of metals by application of optical fields. Our studies indicated that this happens on subfemtosecond time scale and could potentially be used in ultrafast information processing and quantum computation. Related document information

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Spectral line-shape in collinear laser spectroscopy after atomic charge exchange

Collinear laser spectroscopy experiments on fast, neutral beams have been extensively used for studies on short-lived radioactive nuclei, taking advantage of its high sensitivity. The resulting resonance line-shape is known to show significant distortion, due to the energy exchange during the charge-exchange neutralization process, which can cause large systematic uncertainty in the determined centroid. A model for the line shape was constructed and simulated to be compared to measured Al, Si, and Ni hyperfine spectra. It is shown that the distortion is caused mainly by the transfer of electron into many different energy levels in the projectile atom and subsequent decays, rather than secondary inelastic collisions, which were often assumed in the line shape analysis before. Furthermore, the model can also be applied to other projectile–alkali pairs, providing a reliable line-shape with less fitting parameters than conventional phenomenological models.

Atom↗
DOE OSTI2023

In-beam $$\gamma $$-ray spectroscopy of $$^{94}$$Ag

Abstract A recoil-beta-tagging experiment has been performed to study the excited $$T=0$$ T = 0 and $$T=1$$ T = 1 states in the odd–odd $$N=Z$$ N = Z nucleus $$^{94}$$ 94 Ag, populated via the $$^{40}$$ 40 Ca( $$^{58}$$ 58 Ni,1p3n) $$^{94}$$ 94 Ag reaction. The experiment was conducted using the MARA recoil separator and JUROGAM3 array at the Accelerator Laboratory of the University of Jyväskylä. Through correlating fast, high-energy beta decays at the MARA focal plane with prompt $$\gamma $$ γ rays emitted at the reaction target, a number of transitions between excited states in $$^{94}$$ 94 Ag have been identified. The timing characteristics of these transitions confirm that they fall within decay sequences that feed the short-lived $$T=1$$ T = 1 ground state of $$^{94}$$ 94 Ag. The transitions are proposed to proceed within and between the sets of states with $$T=0$$ T = 0 and $$T=1$$ T = 1 . Possible correspondence between some of these transitions from analog states in $$^{94}$$ 94 Pd has been discussed, and shell-model calculations including multipole and monopole electromagnetic effects have been presented, in order to enable predictions of the decay patterns between the $$T=0$$ T = 0 and $$T=1$$ T = 1 states and to allow a theoretical set of Coulomb energy differences to be calculated for the $$A = 94$$ A = 94 $$T=1$$ T = 1 analog states.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Mesoscale interplay among composition heterogeneity, lattice deformation, and redox stratification in single-crystalline layered oxide cathode

Single-crystalline layered oxide materials for lithium-ion batteries are featured by their excellent capacity retention over their polycrystalline counterparts, making them sought-after cathode candidates. Their capacity degradation, however, becomes more severe under high-voltage cycling, hindering many high-energy applications. It has long been speculated that the interplay among composition heterogeneity, lattice deformation, and redox stratification could be a driving force for the performance decay. The underlying mechanism, however, is not well-understood. In this study, we use X-ray microscopy to systematically examine single-crystalline NMC particles at the mesoscale. This technique allows us to capture detailed signals of diffraction, spectroscopy, and fluorescence, offering spatially resolved multimodal insights. Focusing on early high-voltage charging cycles, we uncover heterogeneities in valence states and lattice structures that are inherent rather than caused by electrochemical abuse. These heterogeneities are closely associated with compositional variations within individual particles. Our findings provide useful insights for refining material synthesis and processing for enhanced battery longevity and efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Energy-resolved and time-dependent unimolecular dissociation of hydroperoxyalkyl radicals (˙QOOH)

Hydroperoxyalkyl radicals (˙QOOH) are transient intermediates in the atmospheric oxidation of volatile organic compounds and combustion of hydrocarbon fuels in low temperature (<1000 K) environments. The carbon-centered ˙QOOH radicals are a critical juncture in the oxidation mechanism, but have generally eluded direct experimental observation of their structure, stability, and dissociation dynamics. Recently, this laboratory demonstrated that a prototypical ˙QOOH radical [˙CH 2 (CH 3 ) 2 COOH] can be synthesized by an alternative route, stabilized in a pulsed supersonic expansion, and characterized by its infrared (IR) spectroscopic signature and unimolecular dissociation rate to OH radical and cyclic ether products. The present study focuses on a partially deuterated ˙QOOD analog ˙CH 2 (CH 3 ) 2 COOD, generated in the laboratory by H-atom abstraction from partially deuterated tert-butyl hydroperoxide, (CH 3 ) 3 COOD. IR spectral features associated with jet-cooled and isolated ˙QOOD radicals are observed in the vicinity of the transition state (TS) barrier leading to OD radical and cyclic ether products. Furthermore, the overtone OD stretch (2ν OD ) of ˙QOOD is identified by IR action spectroscopy with UV laser-induced fluorescence detection of OD products. Direct time-domain measurement of the unimolecular dissociation rate for ˙QOOD (2ν OD ) extends prior rate measurements for ˙QOOH. Partial deuteration results in a small increase in the TS barrier predicted by high level electronic structure calculations due to changes in zero-point energies; the imaginary frequency is unchanged. Comparison of the unimolecular decay rates obtained experimentally with those predicted theoretically for both ˙QOOH and ˙QOOD confirm that unimolecular decay is enhanced by heavy-atom tunneling involving simultaneous O–O bond elongation and C–C–O angle contraction along the reaction pathway.

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

Zn acceptors in β-Ga 2 O 3 crystals

Electron paramagnetic resonance (EPR) is used to identify and characterize neutral zinc acceptors in Zn-doped β-Ga 2 O 3 crystals. Two EPR spectra are observed at low temperatures, one from Zn ions at tetrahedral Ga(1) sites (the $Zn$$^{0}_{Ga 1}$ acceptor) and one from Zn ions at octahedral Ga(2) sites (the $Zn$$^{0}_{Ga 2}$ acceptor). These Zn acceptors are small polarons, with the unpaired spin localized in each case on a threefold coordinated oxygen O(I) ion adjacent to the Zn ion. Resolved hyperfine interactions with neighboring 69 Ga and 71 Ga nuclei allow the EPR spectra from the two acceptors to be easily distinguished: $Zn$$^{0}_{Ga 1}$ acceptors interact equally with two Ga(2) ions and $Zn$$^{0}_{Ga 2}$ acceptors interact unequally with a Ga(1) ion and a Ga(2) ion. The as-grown crystals are compensated, with the Zn ions initially present as singly ionized acceptors ($Zn$$^{-}_{Ga 1}$ and $Zn$$^{-}_{Ga 2}$). Exposing a crystal to 325 nm laser light, while being held at 140 K, primarily produces neutral $Zn$$^{0}_{Ga 2}$ acceptors when photoinduced holes are trapped at $Zn$$^{-}_{Ga 2}$ acceptors. This suggests that there may be significantly more Zn ions at Ga(2) sites than at Ga(1) sites. Warming the crystal briefly to room temperature, after removing the light, destroys the EPR spectrum from the shallower $Zn$$^{0}_{Ga 2}$ acceptors and produces the EPR spectrum from the more stable $Zn$$^{0}_{Ga 1}$ acceptors. Furthermore, the $Zn$$^{0}_{Ga 2}$ acceptors decay in the 240–260 K region with a thermal activation energy near 0.65 eV, similar to $Mg$$^{0}_{Ga 2}$ acceptors, whereas the slightly deeper $Zn$$^{0}_{Ga 1}$ acceptors decay close to room temperature with an approximate thermal activation energy of 0.78 eV.

36 MATERIALS SCIENCE↗