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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Quantifying a partial polyamorphic transition in a cerium-based metallic glass during cooling

Cerium-based metallic glasses are prototype polyamorphous systems with pressure-induced polyamorphic transitions extensively reported. Cooling typically has a similar effect on materials as compression with regard to reducing volume. However, previous studies show dramatically different behavior of Ce-based metallic glasses between cooling and compression, whose origin remains unclear. Here, using in situ low-temperature synchrotron high-energy x-ray diffraction, the structural evolution of a Ce68Al10Cu20Co2 metallic glass is accurately determined and analyzed by a structure factor and a reduced pair distribution function (PDF) during cooling from 298 to 83 K. An unusually large linear thermal expansion coefficient is revealed, which is associated with both continuous but inconsistent structural changes between the two subpeaks of the first atomic shell in terms of average bond lengths and coordination numbers. These phenomena are suggested to be attributed to a gradual 4f electron delocalization of only a minimal amount (∼2.6% at 83 K) of Ce atoms by quantitative analysis of the PDF data. However, a previously expected global polymorphic transition from a low-density amorphous state to a high-density amorphous state with an abrupt volume collapse is not observed. Moreover, electrical resistivity also shows a continuous increase during cooling without any sharp change. It is clarified that cryogenic temperatures could facilitate but are not powerful enough alone to trigger a global polymorphic transition in the Ce68Al10Cu20Co2 metallic glass, suggesting a wide distribution of its local atomic environment.

Chen, Zhi↗
DOE OSTI2023

Extracting the excitonic Hamiltonian of a chlorophyll dimer from broadband two-dimensional electronic spectroscopy

We apply Frenkel exciton theory to model the entire Q-band of a tightly bound chlorophyll dimer inspired by the photosynthetic reaction center of photosystem II. The potential of broadband two-dimensional electronic spectroscopy experiment spanning the Qx and Qy regions to extract the parameters of the model dimer Hamiltonian is examined through theoretical simulations of the experiment. We find that the local nature of Qx excitation enables identification of molecular properties of the delocalized Qy excitons. Specifically, we demonstrate that the cross-peak region, where excitation energy is resonant with Qy while detection is at Qx, contains specific spectral signatures that can reveal the full real-space molecular Hamiltonian, a task that is impossible by considering the Qy transitions alone. System–bath coupling and site energy disorder in realistic systems may limit the resolution of these spectral signatures due to spectral congestion.

Chemistry↗
DOE OSTI2023

Mechanisms behind impurity spreading in a channeled, long-leg divertor configuration

One suggested benefit of long-leg, tightly baffled divertor configurations, a common feature included in the designs of many next-generation fusion devices, is access to a delocalized “spread” of impurity radiation along the leg, allowing for a substantial radiation region while maintaining both sufficient distance from the core to prevent pollution of the plasma fuel and avoiding local overheating of the plasma-facing materials. However, it is unclear whether this increased connection length and divertor volume afforded by the long-leg configuration is compatible with impurity transport, and whether it will enable this desired impurity radiation spread at all. Here, the SOLPS 4.3 code is used to assess the distribution of nitrogen and neon impurity radiation in a long-leg, tightly baffled divertor geometry. Further, there is a strong correspondence between the distribution of impurity radiation in the long leg and impurity recycling on the divertor side walls with both the nitrogen simulation set and the neon simulation set, suggesting that impurity spreading along these long legs is due to the interplay between the cross-field transport and associated neutralization of the impurity on the material surfaces.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Photodriven electron-transfer dynamics in a series of heteroleptic Cu(I)–anthraquinone dyads

Solar fuels catalysis is a promising route to efficiently harvesting, storing, and utilizing abundant solar energy. To achieve this promise, however, molecular systems must be designed with sustainable components that can balance numerous photophysical and chemical processes. To that end, here we report on the structural and photophysical characterization of a series of Cu(I)–anthraquinone-based electron donor–acceptor dyads. The dyads utilized a heteroleptic Cu(I) bis-diimine architecture with a copper(I) bis-phenanthroline chromophore donor and anthraquinone electron acceptor. We characterized the structures of the complexes using x-ray crystallography and density functional theory calculations and the photophysical properties via resonance Raman and optical transient absorption spectroscopy. The calculations and resonance Raman spectroscopy revealed that excitation of the Cu(I) metal-to-ligand charge-transfer (MLCT) transition transfers the electron to a delocalized ligand orbital. The optical transient absorption spectroscopy demonstrated that each dyad formed the oxidized copper–reduced anthraquinone charge-separated state. Unlike most Cu(I) bis-phenanthroline complexes where increasingly bulky substituents on the phenanthroline ligands lead to longer MLCT excited-state lifetimes, here, we observe a decrease in the long-lived charge-separated state lifetime with increasing steric bulk. The charge-separated state lifetimes were best explained in the context of electron-transfer theory rather than with the energy gap law, which is typical for MLCT excited states, despite the complete conjugation between the phenanthroline and anthraquinone moieties.

14 SOLAR ENERGY↗
DOE OSTI2024

Noise reduction of stochastic density functional theory for metals

Density Functional Theory (DFT) has become a cornerstone in the modeling of metals. However, accurately simulating metals, particularly under extreme conditions, presents two significant challenges. First, simulating complex metallic systems at low electron temperatures is difficult due to their highly delocalized density matrix. Second, modeling metallic warm-dense materials at very high electron temperatures is challenging because it requires the computation of a large number of partially occupied orbitals. This study demonstrates that both challenges can be effectively addressed using the latest advances in linear-scaling stochastic DFT methodologies. Despite the inherent introduction of noise into all computed properties by stochastic DFT, this research evaluates the efficacy of various noise reduction techniques under different thermal conditions. Our observations indicate that the effectiveness of noise reduction strategies varies significantly with the electron temperature. Furthermore, we provide evidence that the computational cost of stochastic DFT methods scales linearly with system size for metal systems, regardless of the electron temperature regime.

Chemistry↗
DOE OSTI2024

Enhancing the dielectric constant of zwitterionic liquids via dipole moment and anion chemistry

The dielectric constant is a critical parameter in many energy-related applications. Typically, increasing the dielectric constant of soft materials involves adding high dielectric constant polar liquids or inorganic fillers, but there are limitations to this approach due to safety concerns with volatile and flammable solvents and the agglomeration of inorganic fillers. An alternative approach is to add zwitterionic liquids that exhibit exceptionally high dielectric constants with negligible volatility. Here, we report the synthesis of a series of zwitterionic liquids containing an imidazolium cation, exhibiting the highest dielectric constant among all organic molecules (∼350 at 293 K). The cation–anion linkage was tailored in a wide range between three and nine carbons, rendering the zwitterion dipole from 25 to 52 D. Comparing the dielectric constant for zwitterions with different anions (i.e., sulfonylimide, sulfonate, and carboxylate) reveals the beneficial impacts of the delocalized sulfonylimide anion vs the carboxylate anion due to the enlarged molecular dipole and more homogenous liquid morphology. Molecular dipole and liquid morphology are identified as the keys to developing high dielectric constant zwitterionic liquids. The extremely high dielectric constant accessible with the proposed molecular design paves new avenues for developing high dielectric constant zwitterions that act as dielectricizers.

Chemistry↗
DOE OSTI2025

How the choice of exchange–correlation functional affects DFT-based simulations of the hydrated electron

Hydrated electrons are anionic species that are formed when an excess electron is introduced into liquid water. Building an understanding of how hydrated electrons behave in solution has been a long-standing effort of simulation methods, of which density functional theory (DFT) has come to the fore in recent years. The ability of DFT to model the reactive chemistry of hydrated electrons is an attractive advantage over semi-classical methodologies; however, relatively few density functional approximations (DFAs) have been used for the hydrated electron simulations presented in the literature. Here, we simulate hydrated electron systems using a series of exchange–correlation (XC) functionals spanning Jacob’s ladder. We calculate a variety of experimental and other observables of the hydrated electron and compare the XC functional dependence for each quantity. We find that the formation of a stable localized hydrated electron is not necessarily limited to hybrid XC functionals and that some hybrid functionals produce delocalized hydrated electrons or electrons that react with the surrounding water at an unphysically fast rate. Here, we further characterize how different DFAs impact the solvent structure and predicted spectroscopy of the hydrated electron, considering several methods for calculating the hydrated electron’s absorption spectrum for the best comparison between structures generated using different density functionals. None of the dozen or so DFAs that we investigated are able to correctly predict the hydrated electron’s spectroscopy, vertical detachment energy, or molar solvation volume.

Ab-initio molecular dynamics↗
DOE OSTI2026

Bootstrap embedding for interacting electrons in phonon coherent-state mean field

Here, we develop a Fermi–Bose bootstrap embedding framework for the ground state of interacting electrons coupled to a phonon mean field. The method combines bootstrap embedding for correlated electrons with a self-consistent coherent-state mean-field treatment for phonons. This method models the interacting electron–phonon problem as a system of correlated electrons traveling in a self-consistently specified potential landscape, allowing for efficient treatment of large lattice systems. Convergence of the methods for fragment size and total system size is demonstrated for the one-dimensional Hubbard–Holstein model for up to 350 sites. Finite-size scaling is performed to extrapolate to the infinite system size. Benchmarking against the density matrix renormalization group for a small 8-site system at half- and quarter-filling shows an orders-of-magnitude runtime advantage. The comparison further reveals that the method performs best in regimes dominated by localization, such as the Mott insulating phase and the strong-coupling tiny polaron regime, where the local embedding ansatz is still valid. However, due to the mean-field treatment for phonons, we find limitations of our methods in the weakly coupled delocalized region and at the Peierls transition, where quantum phonon fluctuations and long-range kinetic correlations become substantial.

Islam, Shariful [North Carolina State University, ↗
DOE OSTI2020

Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals

Much of the electronic transport, photophysical, or biological functions of molecular materials emerge from intermolecular interactions and associated nanoscale structure and morphology. However, competing phases, defects, and disorder give rise to confinement and many-body localization of the associated wavefunction, disturbing the performance of the material. Here, we employ vibrational excitons as a sensitive local probe of intermolecular coupling in hyperspectral infrared scattering scanning near-field optical microscopy (IR s-SNOM) with complementary small-angle X-ray scattering to map multiscale structure from molecular coupling to long-range order. In the model organic electronic material octaethyl porphyrin ruthenium(II) carbonyl (RuOEP), we observe the evolution of competing ordered and disordered phases, in nucleation, growth, and ripening of porphyrin nanocrystals. From measurement of vibrational exciton delocalization, we identify coexistence of ordered and disordered phases in RuOEP that extend down to the molecular scale. Even when reaching a high degree of macroscopic crystallinity, identify significant local disorder with correlation lengths of only a few nanometers. This minimally invasive approach of vibrational exciton nanospectroscopy and -imaging is generally applicable to provide the molecular-level insight into photoresponse and energy transport in organic photovoltaics, electronics, or proteins.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

From antiferromagnetic and hidden order to Pauli paramagnetism in U M 2 Si 2 compounds with 5 f electron duality

Using inelastic X-ray scattering beyond the dipole limit and hard X-ray photoelectron spectroscopy we establish the dual nature of the U 5 f electrons in U M 2 Si 2 ( M = Pd, Ni, Ru, Fe), regardless of their degree of delocalization. We have observed that the compounds have in common a local atomic-like state that is well described by the U 5 f 2 configuration with the $Γ^{(1)}_1$ and $Γ_2$ quasi-doublet symmetry. The amount of the U 5 f 3 configuration, however, varies considerably across the U M 2 Si 2 series, indicating an increase of U 5 f itineracy in going from M = Pd to Ni to Ru and to the Fe compound. The identified electronic states explain the formation of the very large ordered magnetic moments in UPd 2 Si 2 and UNi 2 Si 2 , the availability of orbital degrees of freedom needed for the hidden order in URu 2 Si 2 to occur, as well as the appearance of Pauli paramagnetism in UFe 2 Si 2 . A unified and systematic picture of the U M 2 Si 2 compounds may now be drawn, thereby providing suggestions for additional experiments to induce hidden order and/or superconductivity in U compounds with the tetragonal body-centered ThCr 2 Si 2 structure.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electronic structure and photophysics of a supermolecular iron complex having a long MLCT-state lifetime and panchromatic absorption

Exploiting earth-abundant iron-based metal complexes as high-performance photosensitizers demands long-lived electronically excited metal-to-ligand charge-transfer (MLCT) states, but these species suffer typically from femtosecond timescale charge-transfer (CT)-state quenching by low-lying nonreactive metal-centered (MC) states. Here, we engineer supermolecular Fe(II) chromophores based on the bis(tridentate-ligand)metal(II)-ethyne-(porphinato)zinc(II) conjugated framework, previously shown to give rise to highly delocalized low-lying 3 MLCT states for other Group VIII metal (Ru, Os) complexes. Electronic spectral, potentiometric, and ultrafast pump–probe transient dynamical data demonstrate that a combination of a strong σ-donating tridentate ligand and a (porphinato)zinc(II) moiety with low-lying π*-energy levels, sufficiently destabilize MC states and stabilize supermolecular MLCT states to realize Fe(II) complexes that express 3 MLCT state photophysics reminiscent of their heavy-metal analogs. The resulting Fe(II) chromophore archetype, FeNHCPZn, features a highly polarized CT state having a profoundly extended 3MLCT lifetime (160 ps), 3 MLCT phosphorescence, and ambient environment stability. Density functional and domain-based local pair natural orbital coupled cluster [DLPNO-CCSD(T)] theory reveal triplet-state wavefunction spatial distributions consistent with electronic spectroscopic and excited-state dynamical data, further underscoring the dramatic Fe metal-to-extended ligand CT character of electronically excited FeNHCPZn. This design further prompts intense panchromatic absorptivity via redistributing high-energy absorptive oscillator strength throughout the visible spectral domain, while maintaining a substantial excited-state oxidation potential for wide-ranging photochemistry––highlighted by the ability of FeNHCPZn to photoinject charges into a SnO 2 /FTO electrode in a dye-sensitized solar cell (DSSC) architecture. Concepts enumerated herein afford opportunities for replacing traditional rare-metal–based emitters for solar-energy conversion and photoluminescence applications.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Tuning the quantumness of simple Bose systems: A universal phase diagram

We present a comprehensive theoretical study of the phase diagram of a system of many Bose particles interacting with a two-body central potential of the so-called Lennard-Jones form. First-principles path-integral computations are carried out, providing essentially exact numerical results on the thermodynamic properties. The theoretical model used here provides a realistic and remarkably general framework for describing simple Bose systems ranging from crystals to normal fluids to superfluids and gases. The interplay between particle interactions on the one hand and quantum indistinguishability and delocalization on the other hand is characterized by a single quantumness parameter, which can be tuned to engineer and explore different regimes. Taking advantage of the rare combination of the versatility of the many-body Hamiltonian and the possibility for exact computations, we systematically investigate the phases of the systems as a function of pressure (P) and temperature (T), as well as the quantumness parameter. Here, we show how the topology of the phase diagram evolves from the known case of 4 He, as the system is made more (and less) quantum, and compare our predictions with available results from mean-field theory. Possible realization and observation of the phases and physical regimes predicted here are discussed in various experimental systems, including hypothetical muonic matter.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

The birth and evolution of solvated electrons in the water

The photo-induced radiolysis of water is an elementary reaction in biology and chemistry, forming solvated electrons, OH radicals, and hydronium cations on fast time scales. Here, we use an optical-pump terahertz-probe spectroscopy setup to trigger the photoionization of water molecules with optical laser pulses at ~400 nm and then time-resolve the transient solvent response with broadband terahertz (THz) fields with a ~90 fs time resolution. We observe three distinct spectral responses. The first is a positive broadband mode that can be attributed to an initial diffuse, delocalized electron with a radius of (22 ± 1) Å, which is short lived (<200 fs) because the absorption is blue-shifting outside of the THz range. The second emerging spectroscopic signature with a lifetime of about 150 ps is attributed to an intermolecular mode associated with a mass rearrangement of solvent molecules due to charge separation of radicals and hydronium cations. After 0.2 ps, we observe a long-lasting THz signature with depleted intensity at 110 cm -1 that is well reproduced by ab initio molecular dynamics. We interpret this negative band at 110 cm -1 as the solvent cage characterized by a weakening of the hydrogen bond network in the first and second hydration shells of the cavity occupied by the localized electron.

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

Annihilation-limited long-range exciton transport in high-mobility conjugated copolymer films

A combination of ultrafast, long-range, and low-loss excitation energy transfer from the photoreceptor location to a functionally active site is essential for cost-effective polymeric semiconductors. Delocalized electronic wavefunctions along π-conjugated polymer (CP) backbone can enable efficient intrachain transport, while interchain transport is generally thought slow and lossy due to weak chain–chain interactions. In contrast to the conventional strategy of mitigating structural disorder, amorphous layers of rigid CPs, exemplified by highly planar poly(indacenodithiophene-co-benzothiadiazole) (IDT-BT) donor-accepter copolymer, exhibit trap-free transistor performance and charge-carrier mobilities similar to amorphous silicon. Here, we report long-range exciton transport in HJ -aggregated IDTBT thin-film, in which the competing exciton transport and exciton–exciton annihilation (EEA) dynamics are spectroscopically separated using a phase-cycling-based scheme and shown to depart from the classical diffusion-limited and strong-coupling regime. In the thin film, we find an annihilation-limited mechanism with ≪100% per-encounter annihilation probability, facilitating the minimization of EEA-induced excitation losses. In contrast, excitons on isolated IDTBT chains diffuse over 350 nm with 0.56 cm 2 s −1 diffusivity, before eventually annihilating with unit probability on first contact. We complement the pump–probe studies with temperature-dependent photocurrent and EEA measurements from 295 K to 77 K and find a remarkable correspondence of annihilation rate and photocurrent activation energies in the 140 K to 295 K temperature range.

Shi, Yuping (ORCID:0000000318289415)↗
DOE OSTI2020

The effect of Cu additions in FePt–BN–SiO 2 heat-assisted magnetic recording media

Structural and chemical order impact magnetic properties of solids, which are governed by spin–orbit coupling and exchange interaction. The ordered L1 0 phase of FePt is a key material to heat-assisted magnetic recording; to enable high storage density, a solid understanding is needed of structural and chemical disorder at small length scales, as well as associated modifications of the electronic band structure. Here, we investigate the effect of boron and copper additions (≲6 mol% Cu) on structural and magnetic properties of L1 0 FePt granular media. Two copper-driven mechanisms, although competing, can lead to improvements in both structural and magnetic properties. In particular, the Cu substitution on the Fe-site leads to a degradation of magnetic properties due to the delocalized electron orbitals originating from a larger Cu d -orbital occupancy. At the same time, Cu substitution leads to an enhanced crystallographic order and consequently magneto-crystalline anisotropy, which offsets the former effect to a large extent. Our study is based on magnetometry, x-ray absorption spectroscopy, ab-initio calculations and a phenomenological theory of disordered FePt granular media. We do not observe a sizable modification to Fe moments and electronic configuration; Cu reveals two different resonances associated with the presence and absence of Cu–B bonds that vary with total Cu concentration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Long-time memory effects in a localizable central spin problem

We study the properties of the Nakajima–Zwanzig memory kernel for a qubit immersed in a many-body localized (i.e. disordered and interacting) bath. We argue that the memory kernel decays as a power law in both the localized and ergodic regimes, and show how this can be leveraged to extract t → ∞ populations for the qubit from finite time (Jt ≤ 10 2 ) data in the thermalizing phase. This allows us to quantify how the long-time values of the populations approach the expected thermalized state as the bath approaches the thermodynamic limit. This approach should provide a good complement to state-of-the-art numerical methods, for which the long-time dynamics with large baths are impossible to simulate in this phase. Additionally, our numerics on finite baths reveal the possibility for unbounded exponential growth in the memory kernel, a phenomenon rooted in the appearance of exceptional points in the projected Liouvillian governing the reduced dynamics. In small systems amenable to exact numerics, we find that these pathologies may have some correlation with delocalization.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Engineering the radiative dynamics of thermalized excitons with metal interfaces

As a platform for optoelectronic devices based on exciton dynamics, monolayer transition metal dichalcogenides (TMDCs) are often placed near metal interfaces or inside planar cavities. While the radiative properties of point dipoles at metal interfaces has been studied extensively, those of excitons, which are delocalized and exhibit a temperature-dependent momentum distribution, lack a thorough treatment. Here, we analyze the emission properties of excitons in TMDCs near planar metal interfaces and explore their dependence on exciton center-of-mass momentum, transition dipole orientation, and temperature. Defining a characteristic energy scale k B T c = ($\hbar k$) 2 /2m (k being the radiative wavevector and m the exciton mass), we find that at temperatures T $\gg$ T c and low densities where the momentum distribution can be characterized by Maxwell-Boltzmann statistics, the modified emission rates (normalized to free space) behave similarly to point dipoles. This similarity in behavior arises due to the broad nature of wavevector components making up the exciton and point dipole emission. On the other hand, the narrow momentum distribution of excitons for T < T c can result in significantly different emission behavior as compared to point dipoles. These differences can be further amplified by considering excitons with a Bose Einstein distribution at high phase space densities, such as in a condensate phase. We find suppression or enhancement of emission relative to the point dipole case by several orders of magnitude. These insights can help optimize the performance of optoelectronic devices that incorporate 2D semiconductors near metal electrodes and can inform future studies of exciton radiative dynamics at low temperatures. Additionally, these studies show that nanoscale optical cavities are a viable pathway to generating long-lifetime exciton states in TMDCs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Hubbard-corrected oxide formation enthalpies without adjustable parameters

A density functional theory (DFT) approach to computing transition metal oxide heat of formation without adjustable parameters is presented. Different degrees of d-electron localization in oxides are treated within the DFT+U approach with site-dependent, first-principles Hubbard U-parameters obtained from linear response theory, and delocalized states in the metallic phases are treated without Hubbard corrections. Comparison of relative stabilities of these differently treated phases is enabled by a local d-electron density matrix-dependent model, which was found by genetic programming against experimental reference formation enthalpies. This mathematically simple model does not explicitly depend on the Hubbard-corrected ionic species and is shown to reproduce the heats of formation of the Mott insulators Ca 2 RuO 4 and Y 2 Ru 2 O 7 within ~3% of experimental results, where the experimental training data did not contain Ru oxides. This newly developed method thus absolves from the need for element-specific corrections fitted to experiments in existing Hubbard-corrected approaches to the prediction of reaction energies of transition metal oxides and metals. The absence of fitting parameters opens up here the possibility to predict relative thermodynamic stabilities and reaction energies involving d-states of varying degree of localization at transition metal oxide interfaces and defects, where site-dependent U-parameters will be particularly important and devising a fitting scheme against experimental data with predictive power would be exceedingly difficult.

transition metal oxides↗