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At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

The Effects of Shockwave Pressures on Ultrafast Vibrational Energy Transfer in BNFF, a Hydrogen-Free Energetic Material

Energy conversion in energetic materials from shock-wave-induced lattice compression to bond breaking critically depends on vibrational coupling and energy transfer between intra- and intermolecular vibrations, though the details of the mechanisms remain unknown. Herein, we indirectly tune the strength of intermolecular interactions in 3,4-bis(3-nitrofurazan-4-yl)furoxan (BNFF), a hydrogen-free energetic material characterized by van der Waals interactions, by applying high static pressure using a diamond anvil cell and monitoring vibrational energy transfer (VET) with ultrafast broadband infrared pump–probe spectroscopy. As BNFF is compressed from ambient pressure to 9 GPa, we find that VET accelerates by ∼ 0.9 ps/GPa. Density functional theory is applied in tandem with experiments to assign mode character and elucidate VET pathways. In conclusion, we find that furazan ring O–N–O vibrations, which are high-frequency detonation-relevant vibrational modes, experience increased sensitivity to lattice compression under shockwave pressures. These findings provide new mechanistic insight into how intermolecular interactions govern the rate and selectivity of VET.

Energy transfer↗
DOE OSTI2023

An efficient protocol for excited states of large biochromophores

Efficient energy transport in photosynthetic antenna is a long-standing source of inspiration for artificial light harvesting materials. However, characterizing the excited states of the constituent chromophores poses a considerable challenge to mainstream quantum chemical and semiempirical excited state methods due to their size and complexity and the accuracy required to describe small but functionally important changes in their properties. In this paper, we explore an alternative approach to calculating the excited states of large biochromophores, exemplified by a specific method for calculating the Q y transition of bacteriochlorophyll a, which we name Chl-xTB. Using a diagonally dominant approximation to the Casida equation and a bespoke parameterization scheme, Chl-xTB can match time-dependent density functional theory’s accuracy and semiempirical speed for calculating the potential energy surfaces and absorption spectra of chlorophylls. We demonstrate that Chl-xTB (and other prospective realizations of our protocol) can be integrated into multiscale models, including concurrent excitonic and point-charge embedding frameworks, enabling the analysis of biochromophore networks in a native environment. We exploit this capability to probe the low-frequency spectral densities of excitonic energies and interchromophore interactions in the light harvesting antenna protein LH2 (light harvesting complex 2). The impact of low-frequency protein motion on interchromophore coupling and exciton transport has routinely been ignored due to the prohibitive costs of including it in simulations. Our results provide a more rigorous basis for continued use of this approximation by demonstrating that exciton transition energies are unaffected by low-frequency vibrational coupling to exciton interaction energies.

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

Insights on the Influence of the Central-Cut Width of the Box Assembly with Removable Component on Its Dynamical Responses

This investigation focuses on the dynamical effects caused by varying the central-cut width within the Box Assembly with Removable Component (BARC) system. The central-cut widths included in this study are a 0.5″ cut, a 0.25″ cut, a thin 0.1″ cut, and a structure that did not have a cut at all. Finite element analysis was conducted to determine the mode shapes and natural frequencies of each of the BARC structures. Structural dynamics experiments were run to examine the effects of the central-cut width on the dynamical responses and nonlinear characteristics of the BARC system. Free vibration testing with an impact hammer was carried out to excite the system and extract the dominant frequencies and directions of the significant responses. A pseudorandom vibration test that allows for the qualitative determination of any nonlinear behavior within the system was performed. This type of behavior can include nonlinear softening, nonlinear hardening, and the most common, nonlinear damping due to the presence of several bolted-joint connections and the possible activation of geometric and inertia nonlinearities. To quantitatively investigate the impacts of the central-cut width on the dynamics of the system, swept sinusoidal testing was conducted. It is determined that almost all systems with central cuts demonstrate the presence of nonlinear softening, but at times, nonlinear hardening trends are seen, particularly in the 0.1″ cut and no-cut systems when testing harmonically. Each of the central-cut systems displays nonlinear damping, with the amount of damping generally increasing as the central cut decreases in size. The effect of the central cut of the BARC system on the mode-switching ability of the system is negligible; however, mode switching takes place when comparing the central-cut configurations to the no-cut one. These results show the significance of accurately measuring the central-cut width and how geometric uncertainty may change the dynamical responses and nonlinear properties of the system.

Padilla, Christopher (ORCID:000900033446732X)↗
DOE OSTI2024

Role of Intermolecular Interactions in Deep Eutectic Solvents for CO 2 Capture: Vibrational Spectroscopy and Quantum Chemical Studies

Recent research and reviews on CO 2 capture methods, along with advancements in industry, have highlighted high costs and energy-intensive nature as the primary limitations of conventional direct air capture and storage (DACS) methods. In response to these challenges, deep eutectic solvents (DESs) have emerged as promising absorbents due to their scalability, selectivity, and lower environmental impact compared to other absorbents. However, the molecular origins of their enhanced thermal stability and selectivity for DAC applications have not been explored before. Therefore, the current study focuses on a comprehensive investigation into the molecular interactions within an alkaline DES composed of potassium hydroxide (KOH) and ethylene glycol (EG). Combining Fourier transform infrared (FT-IR) and quantum chemical calculations, the study reports structural changes and intermolecular interactions induced in EG upon addition of KOH and its implications on CO 2 capture. Experimental and computational spectroscopic studies confirm the presence of noncovalent interactions (hydrogen bonds) within both EG and the KOH-EG system and point to the aggregation of ions at higher KOH concentrations. Additionally, molecular electrostatic potential (MESP) surface analysis, natural bond orbital (NBO) analysis, quantum theory of atoms-in-molecules (QTAIM) analysis, and reduced density gradient-noncovalent interaction (RDG-NCI) plot analysis elucidate changes in polarizability, charge distribution, hydrogen bond types, noncovalent interactions, and interaction strengths, respectively. Evaluation of explicit and hybrid models assesses their effectiveness in representing intermolecular interactions. This research enhances our understanding of molecular interactions in the KOH-EG system, which are essential for both the absorption and desorption of CO 2 . The study also aids in predicting and selecting DES components, optimizing their ratios with salts, and fine-tuning the properties of similar solvents and salts for enhanced CO 2 capture efficiency.

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

Synthesis and Thermal Oxidation Resistance of Boron-Rich Boron–Carbide Material

A boron-rich boron–carbide material (B4+δC) was synthesized by spark plasma sintering of a ball-milled mixture of high-purity boron powder and graphitic carbon at a pressure of 7 MPa and a temperature of 1930 °C. This high-pressure, high-temperature synthesized material was recovered and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Vickers hardness measurements, and thermal oxidation studies. The X-ray diffraction studies revealed a single-phase rhombohedral structure (space group R-3m) with lattice parameters in hexagonal representation as a = 5.609 ± 0.007 Å and c = 12.082 ± 0.02 Å. The experimental lattice parameters result in a value of δ = 0.55, or the composition of the synthesized compound as B4.55C. The high-resolution scans of boron binding energy reveal the existence of a B-C bond at 188.5 eV. Raman spectroscopy reveals the existence of a 386 cm−1 vibrational mode representative of C-B-B linear chain formation due to excess boron in the lattice. The measured Vickers microhardness at a load of 200 gf shows a high hardness value of 33.8 ± 2.3 GPa. Thermal gravimetric studies on B4.55C were conducted at a temperature of 1300 °C in a compressed dry air environment, and its behavior is compared to other high-temperature ceramic materials such as high-entropy transition metal boride. The high neutron absorption cross section, high melting point, high mechanical strength, and thermal oxidation resistance make this material ideal for applications in extreme environments.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Flexocaloric effect in superelastic materials

We present a combined theoretical–experimental study of flexocaloric effects in superelastic materials exhibiting structural transitions. We study a Ginzburg–Landau model combined with a vibrational model for a beam near a ferroelastic transition loaded with a three-point bending setup. We also perform experiments on a Cu–Al–Ni single crystal undergoing a martensitic transition. We measure bent beam profiles, vertical force vs vertical deflection during a slow isothermal process, time evolution of the bending and unbending amplitudes, and the evolution of temperature profiles. We also compute the evolution of heat source and heat sink profiles. Finally, we study the location of acoustic emission events during the bending/unbending experiment. Our observations are consistent with the model predictions and allow us to identify the main physical parameters relevant for flexocaloric applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Crystal structure of calcium-ferrite type NaAlSiO4 up to 45 GPa

Abstract Alkali-rich aluminous high-pressure phases including calcium-ferrite (CF) type NaAlSiO4 are thought to constitute ~20% by volume of subducted mid-ocean ridge basalt (MORB) under lower mantle conditions. As a potentially significant host for incompatible elements in the deep mantle, knowledge of the crystal structure and physical properties of CF-type phases is therefore important to understanding the crystal chemistry of alkali storage and recycling in the Earth’s mantle. We determined the evolution of the crystal structure of pure CF-NaAlSiO4 and Fe-bearing CF-NaAlSiO4 at pressures up to ~45 GPa using synchrotron-based, single-crystal X-ray diffraction. Using the high-pressure lattice parameters, we also determined a third-order Birch-Murnaghan equation of state, with V0 = 241.6(1) Å3, KT0 = 220(4) GPa, and KT0′ = 2.6(3) for Fe-free CF, and V0 = 244.2(2) Å3, KT0 = 211(6) GPa, and KT0′ = 2.6(3) for Fe-bearing CF. The addition of Fe into CF-NaAlSiO4 resulted in a 10 ± 5% decrease in the stiffest direction of linear compressibility along the c-axis, leading to stronger elastic anisotropy compared with the Fe-free CF phase. The NaO8 polyhedra volume is 2.6 times larger and about 60% more compressible than the octahedral (Al,Si)O6 sites, with K0NaO8 = 127 GPa and K0(Al,Si)O6 ~304 GPa. Raman spectra of the pure CF-type NaAlSiO4 sample shows that the pressure coefficient of the mean vibrational mode, 1.60(7) cm–1/GPa, is slightly higher than 1.36(6) cm−1/GPa obtained for the Fe-bearing CF-NaAlSiO4 sample. The ability of CF-type phases to contain incompatible elements such as Na beyond the stability field of jadeite requires larger and less-compressible NaO8 polyhedra. Detailed high-pressure crystallographic information for the CF phases provides knowledge on how large alkali metals are hosted in alumina framework structures with stability well into the lowermost mantle.

Geochemistry & Geophysics↗
DOE OSTI2024

Effect of V Content on Corrosion Behavior of Al-V Alloys Produced by Mechanical Alloying and Subsequent Spark Plasma Sintering

Al-V alloys produced via high-energy ball milling have been reported to show simultaneous improvement of corrosion resistance and mechanical properties compared to traditional Al alloys. In these alloys, V content plays a crucial role in increasing or decreasing the corrosion resistance. Therefore, the effect of V and microstructure on corrosion of high-energy ball milled and subsequently spark plasma sintered Al-xV alloys (x = 2, 5, 10 at%) has been studied. Cyclic potentiodynamic polarization tests and electrochemical impedance spectroscopic analysis revealed the increment of V content up to 5 at% enhanced the corrosion resistance of the alloy. However, highly heterogeneous microstructure in Al-10 at%V resulted in significant localized corrosion over the immersion time. The electrochemical impedance spectroscopy studies over 14 days of immersion revealed underlying corrosion mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Design and Experimental Demonstration of an Additive Manufactured Smart Oxy-Methane Burner for High Pressure and Supercritical Combustion

Pressurized oxy combustion-based systems can improve efficiency by recovering latent heat of the steam in the Flue Gas and achieving 90% CO2 capture. In addition, the novel Directly Heated Supercritical Carbon Dioxide (DH-SCO2) power cycles can achieve high thermal efficiencies and provide nearly full carbon capture. Additionally, due to the reduction of flue gas at higher pressure, smaller system size and capital cost reductions are also possible. Recent thermodynamic analysis of the DH-SCO2 cycle performed by the UTEP research team shows that combustion conditions in the vicinity of 300 bar pressure and 1000-1400 K temperature allow for relatively high system efficiencies while operating within the limit of available combustor materials. However, the realization of a directly heated supercritical power cycle requires combustion systems to operate in supercritical conditions and at temperature far below the blowout limit of conventional flames (above 1500 K). The thermodynamic properties along with the combustion properties and kinetics are unexplored at such conditions. Additionally, the interaction of the supercritical environment with energy components is also unknown. High-pressure combustion tests are performed using a smart burner at some intermediate pressure ranges (<20 bar) to help minimize these knowledge gaps. The knowledge obtained from the high-pressure test will assist in understanding the combustion chamber pressurization mechanism, ignition and flame behavior at the elevated pressure. The obtained data will act as a systematic first step in testing at higher pressures of 100 and 300 bar pressures.The primary purpose of this Dissertation is to demonstrate the operability of a low NOx smart burner for oxy-methane combustion at high pressure (< 20 bar) and scalable up to supercritical conditions. A shear co-axial smart burner is designed with a real-time temperature monitoring capability to understand the burner face interaction at high-pressure conditions. In addition, the burner has four independent injection ports to allow the independent injection of fuel and dilution gases in the combustor. The maximum operating capability of the burner is 575 kWth. The burner was fabricated using a Laser Powder Bed Fusion process with Nickel Alloy 718. A powder removal technology was invented comprising ultrasonic vibration, liquid nitrogen exposure and media blasting to remove powders from internal channels of the burner. The burner operability tests are performed in the high-pressure combustor and the swirl combustor. The high-pressure combustor was used to investigate the burner operability and thermal soak back at different pressurized conditions. The experimental tests in high-pressure combustor up to 275 kWth input resulted in 16.5 bar chamber pressure and 198°C thermal soaks back to the burner. The burner was capable of providing the required thermal input within a 3% deviation range. In addition, soot formation occurred at high-pressure tests. The swirl combustor was used to observe the flame stability of the burner. Flame lift-off was observed for jet velocities above 450 m/s. Additionally, lift-off decreased for low co-flow velocities. CO2 dilution experiments showed increased flame instabilities for all conditions above 50% dilution ratios. At lower thermal inputs, partial flame blow-offs occurred for dilution ratios above 50%. All conditions significantly reduced the flame temperature and increased the flame lift-off height. Finally, a 2nd generation AM smart burner was designed using the knowledge from the 1st generation burner experiments. The 2nd generation burner incorporated two sets of swirlers with 0.9 swirl no. A cooling system was also designed for long-duration tests at higher pressures. The thermal input and division of the burner's power are kept the same as the 1st generation burner. The burner is to be fabricated using nickel-alloy 718 for high-pressure handling capability. The design can sustain at high-pressure conditions up to 100 bar.

Islam, Md Nawshad Arslan↗
DOE OSTI2021

Transforming a Simple Structure Model to Represent a Complex Dynamic System with Unknown Boundary Restraints

Imposing a boundary condition on a structure can significantly alter its dynamic properties. However, sometimes the specifics of the new boundary conditions are not known. When the effects of a boundary condition are uncertain or there is not enough information, engineers need to excite the complex structure to obtain these modified properties. In order to experimentally obtain the new properties, engineers need multiple experiments and many outputs for interpolation in order to sufficiently represent the entire structure. In this study, the researchers attached a stinger to a cantilever beam, acting as a new transverse restraint of unknown properties. This paper presents a conversion expression that predicts the dynamic behavior of any point in the system with the new boundary condition. This expression relies only on one impact hammer experiment with one output and the model of the stinger-free cantilever beam, referred to as the simple structure. Researchers estimated the Transfer Function (TRF) of the beam and compared it with an experimentally measured TRF to validate the method. The mean absolute error of the estimated TRF compared to the experimental TRF is 1.99 dB. This demonstrates the use of the proposed method for estimating unmeasured TRFs in a system with an uncertain boundary condition using a single input, single output (SISO) test and a model of the simple structure.

42 ENGINEERING↗
DOE OSTI2021

Multiphonon diffuse scattering in solids from first principles: Application to layered crystals and two-dimensional materials

Time-resolved diffuse scattering experiments have gained increasing attention due to their potential to reveal nonequilibrium dynamics of crystal lattice vibrations with full momentum resolution. Although progress has been made in interpreting experimental data on the basis of one-phonon scattering, understanding the role of individual phonons can be sometimes hindered by multiphonon excitations. In Ref. [M. Zacharias, H. Seiler, F. Caruso, D. Zahn, F. Giustino, P. C. Kelires, and R. Ernstorfer, Phys. Rev. Lett. 127, 207401 (2021)], we have introduced a rigorous approach for the calculation of the all-phonon inelastic scattering intensity of solids from first-principles. In the present work, we describe our implementation in detail and show that multiphonon interactions are captured efficiently by exploiting translational and time-reversal symmetries of the crystal. We demonstrate its predictive power by calculating the scattering patterns of monolayer molybdenum disulfide (MoS 2 ), bulk MoS 2 , and black phosphorus (bP), and we obtain excellent agreement with our measurements of thermal electron diffuse scattering. Remarkably, our results show that multiphonon excitations dominate in bP across multiple Brillouin zones, while in MoS 2 they play a less pronounced role. We expand our analysis for each system and examine the effect of individual atomic and interatomic vibrational motion on the diffuse scattering signals. We further demonstrate the high-throughput capability of our approach by reporting all-phonon scattering maps of two-dimensional MoSe 2 , WSe 2 , WS 2 , graphene, and CdI 2 , rationalizing in each case the effect of multiphonon processes. As a side point, we show that the special displacement method reproduces the thermally distorted configuration that generates precisely the all-phonon diffuse pattern. In conclusion, the present methodology opens the way for systematic calculations of the scattering intensity in crystals and the accurate interpretation of static and time-resolved inelastic scattering experiments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Temperature-dependent elastic constants of thorium dioxide probed using time-domain Brillouin scattering

Herein we report the adiabatic elastic constants of single-crystal thorium dioxide over a temperature range of 77–350 K. Time-domain Brillouin scattering, an all-optical, non-contact picosecond ultrasonic technique, is used to generate and detect coherent acoustic phonons that propagate in the bulk perpendicular to the surface of the crystal. These coherent acoustic lattice vibrations have been monitored in two hydrothermally grown single-crystal thorium dioxide samples along the (100) and (311) crystallographic directions. The three independent elastic constants of the cubic crystal (C 11 , C 12 , and C 44 ) are determined from the measured bulk acoustic velocities. The longitudinal wave along the (100) orientation provided a direct measurement of C 11 . Measurement of C 44 and C 12 was achieved by enhancing the intensity of quasi-shear mode in a (311) oriented crystal by adjusting the polarization angle relative to the crystal axes. We find the magnitude of softening of the three elastic constants to be ~2.5% over the measured temperature range. Good agreement is found between the measured elastic constants with previously reported values at room temperature, and between the measured temperature-dependent bulk modulus with calculated values. We find that semi-empirical models capturing lattice anharmonicity adequately reproduce the observed trend. We also determine the acoustic Grüneisen anharmonicity parameter from the experimentally derived temperature-dependent bulk modulus and previously reported temperature-dependent values of volumetric thermal expansion coefficient and heat capacity. This work presents measurements of the temperature-dependent elasticity in single-crystal thorium dioxide at cryogenic temperature and provides a basis for testing ab initio theoretical models and evaluating the impact of anharmonicity on thermophysical properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Near-IR Luminescence Tuning in a Series of Chalcogenophene Carboxylate-Decorated Neodymium Dimers

Here, the solvothermal synthesis of a series of Nd dimers decorated with various chalcogenophene carboxylates and 2,2':6',2"-terpyridine of the general formula, [Nd 2 (µ-XC 5 H 3 O 2 ) 2 (XC 5 H 3 O 2 ) 4 (N 3 C 15 H 11 ) 2 (H 2 O) 2 ] where X = O, S, Se, and Te, is reported. The solid-state structures were characterized using single-crystal X-ray diffraction (scXRD) and all the complexes are isomorphous, despite substitution of the heterocyclic chalcogen; phase purity was confirmed via powder X-ray diffraction (pXRD). Vibrational spectroscopy was collected and correlations between chalcogen identity and the binding strength of the carboxylate groups of the chalcogenophene ligands with each metal center were shown to be independent of chalcogen identity. All four complexes displayed Nd(III)-based near-IR luminescence and exhibited ligand-sensitized emission. Varying the chalcogenophene chromophore enabled tuning of the sensitizing triplet state energy level, as evidenced by an 8-fold increase in the sensitization of the TeCA-decorated dimer relative to the other chalcogenophene congeners. This behavior was rationalized by comparing the Nd(III) acceptor and ligand donor states across the series. The donor triplet state of each ligand was estimated via low-temperature (77 K) phosphorescence measurements from 1:1 mixtures with Gd(III); these were found to be 24,631 cm –1 for furan-2-carboxylic acid (FCA), 23,764 cm –1 for thiophene-2-carboxylic acid (TCA), 22,548 cm –1 for selenophene-2-carboxylic acid (SeCA), and 21,186 cm –1 for tellurophene-2-carboxylic acid (TeCA). The greater sensitization efficiency of TeCA is the result of well-matched ligand donor and metal acceptor levels and thus suppression of nonradiative back-energy transfer. More broadly, triplet energy level information for these ligands serves as a guide for future application to other target metals based on the electronic properties necessary to effect efficient sensitization.

Coordination Chemistry↗
DOE OSTI2026

Distinct Kinetic Signatures of Photodesorption from Metal Nanoparticles

Visible photon fluxes can influence the rate and selectivity of heterogeneously catalyzed reactions on metal nanoparticle surfaces. Models describing the influence of photon fluxes have typically introduced photon flux dependent apparent thermal kinetic parameters (reaction orders, activation energies, binding energies, etc.). This has relied on empirical fitting of reaction rate data, making mechanistic interpretations of how photon fluxes influence elementary step rates challenging and inconsistent with fundamental descriptions of photochemistry on metal surfaces developed from surface science studies. Using the CO adsorption–desorption quasi-equilibrium reaction on Pt/Al 2 O 3 catalysts as a model system, we measured steady state adsorbed CO (CO*) coverages under isothermal and isobaric (1 mbar CO) conditions as a function of temperature (473–573 K) and of 440 nm photon flux ((0.1–5.2) × 10 3 # hv Pt site –1 s –1 ) using in situ IR spectroscopy. Steady state CO* coverage on Pt was photon flux dependent with increasing photon flux causing decreasing coverage, consistent with photons driving CO* desorption rates faster than thermal CO* desorption rates. However, photon flux dependent CO* coverages were essentially temperature independent, inconsistent with models that describe photon effects using perturbations to apparent thermal kinetic parameters. Instead, 120 steady state CO* coverages as a function of temperature and photon flux are quantitatively described by a kinetic model in which the overall desorption rate is a summation of independent thermal and photon induced CO* desorption rates. Site-resolved analysis reveals distinct kinetic parameters for photon driven desorption of CO* from well-coordinated, under-coordinated, and highly under-coordinated Pt sites, with temperature-dependent apparent quantum efficiencies (AQE) consistent with temperature dependence of vibrational quanta distribution of adsorbed CO. The rigorous kinetic rate laws for independent photon and thermal driven pathways allow for predictive modeling of the influence of photon fluxes on the rates of CO* desorption under catalytic conditions. Further, the analysis provides evidence that steady state continuous wave photon fluxes can drive desorption/adsorption reactions on metal surfaces out of thermal equilibrium, reconciling surface science observations of molecular photodesorption with applied catalysis. The work establishes a general kinetic framework to be considered for photon driven processes on metals, and defines catalyst, reaction, and photon flux characteristic design principles for breaking Sabatier limitations.

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

Solvent Polarity Independent Symmetry-Breaking Charge Separation in a Slip-Stacked Covalent Terrylene Monoimide Dimer

The design of organic materials capable of efficient photoinduced charge separation in low-polarity environments is a critical challenge for advancing organic photovoltaics. Symmetry-breaking charge separation (SB-CS) offers a promising route to efficient charge separation with minimal energy loss; however, in conventional organic materials this process typically relies on polar solvents to stabilize the charge-separated state. Here, we investigate a slip-stacked terrylene monoimide dimer (TMI 2 ) engineered with intrinsic electronic asymmetry to circumvent this limitation. We demonstrate through a comprehensive suite of ultrafast spectroscopic techniques that TMI 2 undergoes remarkably efficient SB-CS regardless of solvent polarity enabled by the permanent dipole moment of TMI and the accessible intramolecular charge-transfer (ICT) character of its monomer units. Furthermore, analysis of vibronic coherences reveals that the initial state mixing is actively driven by a 193 cm –1 intermolecular mode, while the final SB-CS state is marked by a distinct vibrational fingerprint of the radical ion pair product. Our findings reveal how the intrinsic electronic asymmetry of the TMI monomers that constitute TMI 2 creates an efficient charge separation pathway that precludes the need for external stabilization from a polar solvent. Here, this work establishes a powerful molecular design principle for leveraging intrinsic monomeric asymmetry to achieve efficient charge separation in low-dielectric environments, with significant implications for the development of next-generation organic optoelectronic materials.

Aromatic compounds↗
DOE OSTI2020

High Thermoelectric Performance and Defect Energetics of Multipocketed Full Heusler Compounds

We report a first-principles density-functional study of electron-phonon interactions in and thermoelectric transport properties of the full Heusler compounds Sr 2 BiAu and Sr 2 SbAu. Our results show that ultrahigh intrinsic bulk thermoelectric performance across a wide range of temperatures is physically possible and point to the presence of multiply degenerate and highly dispersive carrier pockets as the key factor for achieving this. Sr 2 BiAu, which features ten energy-aligned low-effective-mass pockets (six along Γ-X and four at L), is predicted to deliver n-type zT=0.4-4.9 at T=100-700 K. Comparison with the previously investigated compound Ba 2 BiAu shows that the additional L pockets in Sr 2 BiAu significantly increase its low-temperature power factor to a maximum value of 12 mW m -1 K -2 near T=300 K. However, at high temperatures the power factor of Sr 2 BiAu drops below that of Ba 2 BiAu because the L states are heavier and subject to strong scattering by phonon deformation, as opposed to the lighter Γ-X states, which are limited by polar-optical scattering. Sr2SbAu is predicted to deliver a lower n-type zT=3.4 at T=750 K due to appreciable misalignment between the L and Γ-X carrier pockets, generally heavier scattering, and a slightly higher lattice thermal conductivity. Soft acoustic modes, which are responsible for the low lattice thermal conductivity, also increase the vibrational entropy and high-temperature stability of these Heusler compounds, suggesting that their experimental synthesis may be feasible. The dominant intrinsic defects are found to be Au vacancies, which drive the Fermi level towards the conduction band and work in favor of n-doping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Structural phase purification of bulk HfO 2 :Y through pressure cycling

We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO 2 :7%Y from the mixed monoclinic ( P 2 1 / c ) + antipolar orthorhombic ( Pbca ) phase to pure antipolar orthorhombic ( Pbca ) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the Pbca metastable state at 300 K. Compression also drives polar orthorhombic ( P c a 2 1 ) hafnia into the tetragonal ( P 4 2 / n m c ) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape. The fact that pressure allows us to stabilize targeted metastable structures with less Y stabilizer is important to preserving the flat phonon band physics of pure HfO 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Flexocaloric effect near a ferroelastic transition

A Ginzburg-Landau model embedded into a vibrational model is used to study the flexocaloric effect in a beam near a ferroelastic transition. The caloric response upon bending is characterized by the isothermal entropy change and the adiabatic temperature change of the beam. Here, we obtain a larger response relative to the strength of the applied forces at temperatures slightly above the transition temperature. It is also obtained that the maximum caloric response is almost linear with the bending angle of the beam, whereas the relation between the bending angle and the applied forces is highly nonlinear. Small hysteresis associated with the phase transition is obtained for sufficiently large bending forces due to the existence of a critical point in the temperature-stress phase diagram of the ferroelastic material. Finally, the microstructure changes with bending in the beam are consistent with previous experimental observations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗