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DOE OSTI2021

Magnetoelastic coupling and spin contributions to entropy and thermal transport in biferroic yttrium orthochromite

Direct engineering of material properties through exploitation of spin, phonon, and charge-coupled degrees of freedom is an active area of development in materials science. However, the relative contribution of the competing orders to controlling the desired behavior is challenging to decipher. In particular, the independent role of phonons, magnons, and electrons, quasiparticle coupling, and relative contributions to the phase transition free energy largely remain unexplored, especially for magnetic phase transitions. Here, we study the lattice and magnetic dynamics of biferroic yttrium orthochromite using Raman, infrared, and inelastic neutron spectroscopy techniques, supporting our experimental results with first-principles lattice dynamics and spin-wave simulations across the antiferromagnetic transition at T N ~ 138 K. Spectroscopy data and simulations together with the heat capacity (C p ) measurements, allow us to quantify individual entropic contributions from phonons (0.01 ± 0.01k B atom -1 ), dilational (0.03 ± 0.01k B atom -1 ), and magnons (0.11 ± 0.01k B atom -1 ) across TN. High-resolution phonon measurements conducted in a magnetic field show that anomalous T-dependence of phonon energies across TN originates from magnetoelastic coupling. Additionally, phonon scattering is primarily governed by the phonon–phonon coupling, with little contribution from magnon–phonon coupling, short-range spin correlations, or magnetostriction effects; a conclusion further supported by our thermal conductivity measurements conducted up to 14 T, and phenomenological modeling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

VLBI Data Processing on Coronal Radio-sounding Experiments of Mars Express

The ESA’s Mars Express solar corona experiments were performed at two solar conjunctions in the years 2015 and 2017 by a number of radio telescopes in the European VLBI Network. This paper presents the methods to measure the frequency and phase fluctuations of the spacecraft radio signal, and the applications to study the characteristics of the plasma turbulence effects on the signal at a single station and at multiple stations via cross correlation. The power spectra of the frequency fluctuations observed between 4.9 and 76.3 R {sub s} have a power-law shape close to a Kolmogorov spectrum over the frequency interval ν {sub lo} < ν < ν {sub up}, where the nominal value of ν {sub lo} is set to 3 mHz and ν {sub up} is in the range of 0.03–0.15 Hz. The rms of the frequency fluctuations is presented as a function of the heliocentric distance. Furthermore, we analyze the variations of the electron column density fluctuations at solar offsets 4.9 R {sub s} and 9.9 R {sub s} and the cross-correlation products between the VLBI stations. The power density of the differential fluctuations between different stations decreases at ν < 0.01 Hz. Finally, the fast flow speeds of solar wind >700 km s{sup -1} are derived from the cross correlation of frequency fluctuations at ν < 0.01 Hz. The fast flow speeds of solar wind correspond to the high heliolatitude of the coronal region that the radio rays passed. The VLBI observations and analysis methods can be used to study the electron column density fluctuations and the turbulence at multiple spatial points in the inner solar wind by providing multiple lines of sight between the Earth and the spacecraft.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2021

Adiabatic behavior of an elliptical vortex in a time-dependent external strain flow

The adiabatic behavior of two-dimensional (2D) fluid vortices subject to slowly varying, time-dependent external strain flows is studied theoretically, and experimentally using magnetized non-neutral electron plasmas. Here the E × B drift dynamics of the electrons perpendicular to the magnetic field are analogous to the motion of fluid vorticity under the 2D Euler equations describing ideal fluids. A low-dimensional elliptical vortex patch model is used along with a WKB approximation to derive a formula for the breaking of an adiabatic invariant due to the changing external flow. The invariant is interpreted as the amplitude of a perturbative oscillation about a stable fixed point corresponding to a steady elliptical vortex. Smooth, hyperbolic tangent and piecewise linear ramp functions are considered for the external strain time dependence. Standard exponential breaking is observed in the former case, whereas the latter exhibits a power-law breaking curve with periodic modulation. It is found that a driving term in the equations of motion contributes the majority of the breaking whereas the frequency variation plays a weaker, but significant role. The experimental data agree closely with the theoretical model. The most significant deviation is due to inviscid damping behavior associated with the smooth edges of the experimental vortices, which tends to reduce the amplitude of the oscillation. Finally, the results are compared and contrasted with other related experimental, numerical, and theoretical work.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2003

164-GHz MMIC HEMT Frequency Doubler

A monolithic microwave integrated circuit (MMIC) that includes a high-electron-mobility transistor (HEMT) has been developed as a prototype of improved frequency doublers for generating signals at frequencies greater than 100 GHz. Signal sources that operate in this frequency range are needed for a variety of applications, notably including general radiometry and, more specifically, radiometric remote sensing of the atmosphere. Heretofore, it has been common practice to use passive (diode-based) frequency multipliers to obtain frequencies greater than 100 GHz. Unfortunately, diode-based frequency multipliers are plagued by high DC power consumption and low conversion efficiency. Moreover, multiplier diodes are not easily integrated with such other multiplier-circuit components as amplifiers and oscillators. The goals of developing the present MMIC HEMT frequency doubler were (1) to utilize the HEMT as an amplifier to increase conversion efficiency (more precisely, to reduce conversion loss), thereby increasing the output power for a given DC power consumption or, equivalently, reducing the DC power consumption for a given output power; and (2) to provide for the integration of amplifier and oscillator components on the same chip. The MMIC frequency doubler (see Figure 1) contains an AlInAs/GaInAs/InP HEMT biased at pinch-off to make it function as a class-B amplifier (meaning that it conducts in half-cycle pulses). Grounded coplanar waveguides (GCPWs) are used as impedance-matching transmission lines. Air bridges are placed at discontinuities to suppress undesired slot electromagnetic modes. Another combination of GCPWs also serves both as a low-pass filter to suppress undesired oscillations at frequencies below 60 GHz and as a DC blocker. Large decoupling capacitors and epitaxial resistors are added in the drain and gate lines to suppress bias oscillations. At the output terminal, the fundamental frequency is suppressed by a quarter-wave open stub, which presents a short circuit at the fundamental frequency and an open circuit at the second harmonic. At an input power of 7 mW, the output power and conversion loss at an output frequency of 164 GHz were found to be 5 dBm (approximately equal to 3.2 mW) and 2 dB, respectively, with a 3-dB output-power bandwidth of 14 GHz. This is the best performance reported to date for an MMIC HEMT frequency doubler above 100 GHz.

Samoska, Lorene↗

DOE OSTI2022

Fully Distributed Multi-Material Magnetic Sensing Structures for Multiparameter DAS Applications

This dissertation demonstrates the first of its kind distributed magnetic field sensor based on a fiber optic distributed acoustic sensing (DAS) scheme. Ferromagnetic nickel and Metglas® were dispersed internally within a fiber optic preform and then drawn on an in-house fiber optic draw tower to lengths in the kilometers. Due to the close proximity of the ferromagnetic metals and fiber optic core, the magnetostrictive strain response of the ferromagnetic materials when exposed to a magnetic field would perturbate within the fiber cladding and transfer that strain, internally, to the fiber optic core. Strain resulting from the magnetostrictive effect allows the DAS based sensor to accurately translate strain into readable magnetic field data. Due to the high sensitivity seen in this sensor design, multiparameter sources, acoustic and magnetic fields, were tested and validated and a three dimensional magnetic-field vector sensor was proposed. Numerical analysis of the novel sensor design was first implemented using COMSOL Multiphysics, where inputs such as magnetostrictive element shape, size, distance, and number were first investigated. Upon optimizing system constraints, the sensor design was further modified such that single mode operation was consistent across multiple fiber draws while retaining high strain transfer from the ferromagnetic elements to the fiber optic core. Ferromagnetic material selection was evaluated as a function of the saturation magnetostriction constants and a total of 4 modules were used to fully characterize the complex physics involved in this sensor design. All fabrication and testing were performed in-house using a full scale 3-story fiber draw tower and custom environmental testing stations to imitate naturally occurring events such as magnetic or acoustic point sources. A unique stacking method was used to embed ferromagnetic nickel and Metglas® into a fiber optic preform which when combined with a custom fiber draw process resulted in consistent multi-material fibers drawn to lengths of 1-km. In-house testing facilities included different types of electromagnetic generators, in addition to a soil test bed, and an outdoor test bed which allowed 100 meters of fiber to be tested simultaneously. All tested sensors demonstrated high strain transfer capabilities on the order of 0.01-10 μϵ depending on the materials used, ferromagnetic rod number, and core to metal spacing. Due to the sensitivity of the system the difference between AC and DC was distinct, and directional magnetostriction was studied. Transverse and longitudinal magnetic wave propagation was controlled through a solenoid and rectangular Helmholtz coil, both built in-house. A three-dimensional magnetic field vector sensor was proposed due to the success of the magnetic field sensor, and a design was proposed and initially tested to validate direction as a function of field strength and distance. To summarize, this dissertation explores the first fully distributed magnetic field sensor using DAS based techniques and one of the first multi-material fiber draw processes which can produce consistent single mode fiber up to 1-km. Due to extensive FEA modeling, multiple iterations of the magnetic sensor were fully characterized and an equation describing the relationship between sensor design and strain transfer has been created and validated experimentally. Multi-parameter tests including acoustic and magnetic fields were implemented and an algorithm was developed to separate the mixed signals. Finally, a test was performed to demonstrate the feasibility of sensing magnetic fields directionally. Cumulative results demonstrate a high-quality sensor alternative to current designs which may surpass other magnetic sensors due to innate multi-parameter capabilities, in addition to the inexpensive production cost and extremely long operating lengths.

02 PETROLEUM↗

DOE OSTI2018

Liquid Structure of Shock-Compressed Hydrocarbons at Megabar Pressures

We present here results for the ionic structure in hydrocarbons (polystyrene, polyethylene) that were shock compressed to pressures of up to 190 GPa, inducing rapid melting of the samples. The structure of the resulting liquid is then probed using in situ diffraction by an x-ray free electron laser beam, demonstrating the capability to obtain reliable diffraction data in a single shot, even for low-Z samples without long range order. The data agree well with ab initio simulations, validating the ability of such approaches to model mixed samples in states where complex interparticle bonds remain, and showing that simpler models are not necessarily valid. While the results clearly exclude the possibility of complete carbon-hydrogen demixing at the conditions probed, they also, in contrast to previous predictions, indicate that diffraction is not always a sufficient diagnostic for this phenomenon.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Open-source library for performance-portable neutrino reaction rates: Application to neutron star mergers

A realistic and detailed description of neutrinos in binary neutron star (BNS) mergers is essential to build reliable models of such systems. To this end, we present bns_nurates, a novel open-source numerical library designed for the efficient on-the-fly computation of neutrino interactions, with particular focus on regimes relevant to BNS mergers. bns_nurates targets a higher level of accuracy and realism in the implementation of commonly employed reactions by accounting for relevant microphysics effects on the interactions, such as weak magnetism and mean field effects. It also includes the contributions of inelastic neutrino scattering off electrons and positrons and (inverse) nucleon decays. Finally, it offers a way to reconstruct the neutrino distribution function in the framework of moment-based transport schemes. As a first application, we compute both energy-dependent and energy-integrated neutrino emissivities and opacities for conditions extracted from a BNS merger simulation with m1 transport scheme. We find some qualitative differences in the results when considering the impact of the additional relevant reactions and of microphysics effects. For example, neutrino-electron/positron scattering reactions are important for the energy exchange of heavy-type neutrinos as they do not undergo semileptonic charged-current processes, when μ± are not accounted for. Moreover, weak magnetism and mean field effects can significantly modify the contribution of β processes for electron-type (anti)neutrinos, increasing at the same time the importance of (inverse) neutron decays. Here, the improved treatment for the reaction rates also modifies the conditions at which neutrinos decouple from matter in the system, potentially affecting their emission spectra.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS2001

Resonance Scattering of Fe XVII X-Ray and EUV Lines

Over the years a number of calculations have been carried out to derive intensities of various X-ray and EUV lines in Fe XVII to compare with observed spectra. The predicted intensities have not agreed with solar observations, particularly for the line at 15.02 Angstroms; resonance scattering has been suggested as the source for much of the disagreement. The atomic data calculated earlier used seven configurations, 2s(sup 2) 2p(sup 6),2s(sup 2) 2p(sup 5)3s, 2s(sup 2) 2p(sup 5)3p, 2s(sup 2)2p(sup 5)3d, 2s2 p(sup 6)3s, 2s2p(sup 6)3p, and 2s2p(sup 6)3d, having n=3 orbitals and the scattering calculations in the distorted wave approximation were carried out only for incident energies above the threshold of the highest fine-structure level. These calculations have now been extended to thirteen configurations by adding six more configurations having n=4 orbitals, namely 2s(sup 2) 2p(sup 5)4s, 2s(sup 2) 2p(sup 5)4p, 2s(sup 2) 2p(sup 5)4d, 2s2p(sup 6)4s, 2s2p(sup 6)4p, and 2s2p(sup 6)4d, giving rise to 73 fine structure levels. The scattering calculations are carried out below as well as above the threshold of the highest fine-structure level. The incident energies below the threshold are 55.8, 65, 70, and 76 Ry and those above are 85, 127.5, 170, 212.5, 255, 340, and 425 Ry. The collision strengths are calculated up to total angular momentum L(sup T) = 33. Level populations and intensity ratios are calculated at various electron temperatures and densities. It is not possible to predict how the ratios would change when configurations with n=5 and 6 orbitals are added but some estimates have been made for a few transitions by Liedhal, who indicates an asymptotic convergence when n=5 and 6 orbitals are added. These improved calculations of Fe XVII change the intensity ratios compared to those obtained earlier, bringing the optically thin F(15.02)/F(16.78) ratio and several other ratios closer to the observed values: However, some disagreement with the solar observations still persists, even though the agreement of the presently calculated optically thin F(15.02)/F(15.26) ratio with the experimental results of Brown et al. and Laming et al. has improved. Some of the remaining discrepancy is still thought to be the effect of opacity, which is consistent with expected physical conditions for solar sources. EUV intensity ratios are also calculated and compared with observations. Level populations and intensity ratios are calculated, as a function of column density of Fe XVII, in the slab and cylindrical geometries. As found previously, the predicted intensities for the resonance lines at 15.02 and 15.26 Angstroms exhibit initial increases in flux relative to the forbidden line at 17.10 Angstroms and the resonance line at 16.78 Angstroms as optical thickness increases. The same behavior is predicted for the lines at 12.262 and 12.122 Angstroms. Predicted intensities for some of the allowed EUV lines are also affected by opacity.

Bhatia, A. K.↗

DOE OSTI2019

GW170817 implications on the frequency and damping time of $f$-mode oscillations of neutron stars

Within a minimum model for neutron stars consisting of nucleons, electrons, and muons at $β$ equilibrium using about a dozen equations of state (EOS) from microscopic nuclear many-body theories and 40000 EOSs randomly generated using an explicitly isospin-dependent parametric EOS model for high-density neutron-rich nucleonic matter within its currently known uncertainty range, we study correlations among the $f$-mode frequency, its damping time and the tidal deformability as well as the compactness of neutron stars. Except for quark stars, both the $f$-mode frequency and damping time of canonical neutron stars are found to scale with the tidal deformability independent of the EOSs used. Applying the constraint on the tidal deformability of canonical neutron stars $Λ_{1.4} = 190^{+390}_{-120}$ extracted by the LIGO+VIRGO Collaborations from their improved analyses of the GW170817 event, the $f$-mode frequency and its damping time of canonical neutron stars are limited to 1.67–2.18 kHz and 0.155–0.255 s, respectively, providing a useful guidance for the ongoing search for gravitational waves from the $f$-mode oscillations of isolated neutron stars. Finally, assuming either or both the $f$-mode frequency and its damping time will be measured precisely in future observations with advanced gravitational wave detectors, we discuss how information about the mass and/or radius as well as the still rather elusive nuclear symmetry energies at suprasaturation densities may be extracted.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2018

Applied Quantum Physics for Novel Quantum Computation Approaches: an Update

Quantum information processing is a critical part of the development of future computers, quantum computers, and quantum algorithms, where elementary particles such as photons and electrons can be applied in optomagnetic or optoelectronic devices. The computational physics behind these emerging approaches is also experiencing dramatic developments. In this paper I report on the most recent mathematical basics for quantum algorithms and quantum computing approaches. Some of these described approaches show intriguing methods for determining the states and wavefunction properties for anyons, bosons, and fermions in quantum wells that have been developed in the last years. The study also shows approaches based on N-quantum states and the reduced 1- and 2-fermion picture, which can be used for developing models for anyons and multi-fermionic states in quantum algorithms. Also, antisymmetry and generalized Pauli constraints have been given particular emphasis and include establishing a basis for pinning and quasipinning for exploring the symmetric states of many-fermionic subsets, as a foundation for quantum information processing, and are here briefly revisited. This study summarizes the developments in recent years of an advanced and important field for future computational techniques.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2022

Development of slurry targets for high repetition-rate x-ray free electron laser experiments

Combining an x-ray free electron laser with a high-power laser driver enables the study of equations-of-state, high strain-rate deformation processes, structural phase transitions, and transformation pathways as a function of pressure to hundreds of GPa along different thermodynamic compression paths. Future high repetition-rate laser operation will enable data to be accumulated at >1 Hz, which poses a number of experimental challenges, including the need to rapidly replenish the target. Here, we present a combined shock compression and an x-ray diffraction study on epoxy (50% vol.)-crystalline grains (50% vol.) slurry targets, which can be fashioned into extruded ribbons for high repetition-rate operation. For shock-loaded NaCl-slurry samples, we observe pressure, density, and temperature states within the embedded NaCl grains consistent with observations from shock-compressed single-crystal NaCl.

47 OTHER INSTRUMENTATION↗

DOE OSTI2025

Broadband THz Modulation via Solid–State Organic Electrochemical Devices

The sub-Terahertz and Terahertz bands play a critical role in next-generation wireless communication and sensing technologies, thanks to the large amount of available bandwidth in this spectral regime. While long-wavelength (microwave to mm-Wave) and short-wavelength (near-infrared to ultraviolet) devices are well-established and studied, the sub-THz to THz regime remains relatively underexplored and underutilized. Traditional approaches used in the aforementioned spectral regions are more difficult to replicate in the THz band, leading to the need for the development of novel devices and structures that can manipulate THz radiation effectively. Herein a novel organic, solid-state electrochemical device is presented, capable of achieving modulation depths of over 90% from ≈500 nm of a conducting polymer that switches conductivity over a large dynamic range upon application of an electronically controllable external bias. The stability of such devices under long-term, repeated voltage switching, as well as continuous biasing at a single voltage, is also explored. Switching stabilities and long-term bias stabilities are achieved over two days for both use cases. Additionally, both depletion mode (always “ON”) and accumulation mode (always “OFF”) operation are demonstrated. These results suggest applications of organic electrochemical THz modulators in large area and flexible implementations.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Electronic properties of a Weyl semimetal in crossed magnetic and electric fields

The study of Weyl semimetals is one of the most challenging problems of condensed matter physics. These materials exhibit interesting properties in a magnetic field. In this work, we investigate the Landau bands and the density of states (DOS) oscillations in a Weyl semimetal in crossed magnetic and electric fields. An expression is obtained for the energy spectrum of the system using the following three different methods: an algebraic approach, a Lorentz shift-based approach, and a quasi-classical approach. It is interesting that the energy spectrum calculated in terms of the quasi-classical approach coincides with the spectrum obtained using the microscopic approaches. An electric field is shown to change the Landau bands radically. In addition, the classical motion of a three-dimensional Dirac fermion in crossed fields is studied. In the case of a Dirac spectrum, the longitudinal (with respect to magnetic field) component of momentum (p{sub z} ǁ H) is shown to be an oscillating function of the magnetic field. When the electric field is v⊥H/c, the Landau levels collapse and the motion becomes fully linear in an unusual manner. In this case, the wavefunction of bulk states vanishes and only states with p{sub z} = 0 are retained. An electric field affects the character of DOS oscillations. An analytical expression is obtained for the quantum capacitance in crossed fields in the cases of strong and weak electric fields. Thus, an electric field is an additional parameter for adjusting the diamagnetic properties of Weyl semimetals.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2025

Spatial Signatures of Electron Correlation in Least-Squares Tensor Hypercontraction

Least Squares Tensor Hypercontraction (LS-THC) has received some attention in recent years as an approach to reduce the significant computational costs of wavefunc- tion based methods in quantum chemistry. However, previous work has demonstrated that the LS-THC factorization performs disproportionately worse in the description of wavefunction components (e.g. cluster amplitudes T 2 ) than Hamiltonian compo- nents (e.g. electron repulsion integrals (pq|rs)). This work develops novel theoretical methods to study the source of these errors in the context of the real-space T 2 kernel, and reports, for the first time, the existence of a “correlation feature” in the errors of the LS-THC representation of the “exchange-like” correlation energy EX and T 2 that is remarkably consistent across ten molecular species, three correlated wavefunctions, and four basis sets. This correlation feature portends the existence of a “pair-point kernel” missing in the usual LS-THC representation of the wavefunction, which critically depends upon pairs of grid points situated close to atoms and with inter-pair distances between one and two Bohr radii. These findings point the way for future LS-THC developments to address these shortcomings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Constraining Relativistic Bow Shock Properties in Rotation-powered Millisecond Pulsar Binaries

Multiwavelength follow-up of unidentified Fermi sources has vastly expanded the number of known galactic-field “black widow” and “redback” millisecond pulsar binaries. Focusing on their rotation-powered state, we interpret the radio to X-ray phenomenology in a consistent framework. We advocate the existence of two distinct modes differing in their intrabinary shock orientation, distinguished by the phase centering of the double-peaked X-ray orbital modulation originating from mildly relativistic Doppler boosting. By constructing a geometric model for radio eclipses, we constrain the shock geometry as functions of binary inclination and shock standoff R {sub 0}. We develop synthetic X-ray synchrotron orbital light curves and explore the model parameter space allowed by radio eclipse constraints applied on archetypal systems B1957+20 and J1023+0038. For B1957+20, from radio eclipses the standoff is R {sub 0} ∼ 0.15–0.3 fraction of binary separation from the companion center, depending on the orbit inclination. Constructed X-ray light curves for B1957+20 using these values are qualitatively consistent with those observed, and we find occultation of the shock by the companion as a minor influence, demanding significant Doppler factors to yield double peaks. For J1023+0038, radio eclipses imply R {sub 0} ≲ 0.4, while X-ray light curves suggest 0.1 ≲ R {sub 0} ≲ 0.3 (from the pulsar). Degeneracies in the model parameter space encourage further development to include transport considerations. Generically, the spatial variation along the shock of the underlying electron power-law index should yield energy dependence in the shape of light curves, motivating future X-ray phase-resolved spectroscopic studies to probe the unknown physics of pulsar winds and relativistic shock acceleration therein.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

Hot-Carrier Injection and Millisecond Charge Separation from a Robust Heteroleptic Iron(II) Chromophore Immobilized on TiO 2

The synthesis, spectroscopic characterization, computational analysis, and photoelectrochemical behavior of a new iron-based chromophore, [(Cpy) 2 Fe- (deeb)](PF 6 ) 2 (Fe(Cpy) 2 (deeb)), where Cpy is 1-methyl-3-(2-pyridyl)imidazole and deeb is 4,4’-(CO 2 CH 2 CH 3 ) 2 -2,2’-bipyridine, is reported. Electrochemically reversible waves assigned to a metal-centered E o (Fe III/II ) = +0.48 and a ligand-centered E o (Fe 2+/+ ) = −1.47 V vs Fc +/0 reduction were evident in cyclic voltammetry measurements. The combination of a strong σ-donor and a π-acceptor lowered the energy of the metal-toligand charge-transfer (MLCT) excited state relative to the metal-centered state. Two MLCT transitions appear in the visible region at 424 and 580 nm. TDDFT calculations revealed that the lower-energy band was well formulated as Fe(II)→deeb, and the higher-energy transition was charge transfer to both the deeb and Cpy ligands. Resonance Raman spectroscopy supports these findings showing enhanced deeb vibrational modes with 532 nm excitation, both deeb and Cpy modes with 473 nm excitation, and exclusively Cpy with 405 nm excitation. Ultrafast spectroscopy reveals a short-lived (∼2 ps) MLCT excited state and a longer-lived (∼20 ps) metal-centered state. Efficient methods to deprotect the ester groups and anchor the complex to mesoporous TiO 2 (anatase) thin films in high surface coverages, Fe(Cpy) 2 (dcb)|TiO 2 σ = 3 × 10 −8 mol/cm 2 , were established. Pulsed light excitation of Fe(Cpy) 2 (dcb)|TiO 2 resulted in rapid excited state injection (k inj > 10 8 s −1 ) and formation of a charge-separated state, Fe III (Cpy) 2 (dcb)|TiO 2 (e), which persists on the millisecond time scale before returning cleanly to the ground state with secondorder kinetics. Injection yields measured 50 ns after light excitation were found to double from Φ = 0.15 with green (532 nm) light to 0.30 with blue (457 nm) light excitation. Incident photon-to-current efficiency (% IPCE) measurements as a function of excitation wavelength in a 0.5 M LiI/I 2 /CH 3 CN electrolyte provide clear evidence for band-selective “hot carrier” injection from the remote Cpy-localized excited state. Collectively, the spectroscopic and photoelectrochemical data indicate that a semiconductor can intercept hot electrons from iron chromophores even when the excited-state dipole is oriented away from the surface-anchoring ligand.

Charge transfer↗

DOE OSTI2026

Charge correlations and magnetoelastic coupling in intercalated transition metal dichalcogenides

The large van der Waals gap in transition metal dichalcogenides (TMDs) offers an avenue to tune the ground state of 2D materials through the intercalation of magnetic atoms. Here, we investigate the charge correlations in Fe 1/3 ⁢TaS 2 , Co 1/3 ⁢TaS 2 , and Fe 0.35 ⁢NbS 2 by combining angle-resolved photoemission spectroscopy (ARPES), x-ray scattering, magnetometry, and density functional theory (DFT). We find that, while short-range charge fluctuations develop in Ta-based compounds, Fe 0.35 ⁢NbS 2 exhibits long-range charge order which is strongly coupled with magnetic order and tunable by external magnetic field. Our electronic structure analysis reveals that intercalation reconstructs the Fermi surface via charge transfer and band renormalization, yet does not generate the nesting conditions compatible with the observed ordering vectors. Complementary phonon calculations further exclude a conventional electron-phonon origin of charge order. Together, these results establish magnetoelastic coupling as the dominant mechanism behind charge ordering in Fe 0.35 ⁢NbS 2 and highlight the contrasting role of Nb and Ta hosts in stabilizing correlated ground states in intercalated TMDs.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Energy Frontier Research Centers: Center for the Computational Design of Functional Layered Materials (CCDM) August 1, 2014 - July 31, 2018; Center for Complex Materials from First Principles (CCM) August 1, 2018 - July 31, 2021 (Final Report)

The mission of the DOE Energy Frontier Research Centers CCDM (2014-2018) and CCM (2018-2021) was to theoretically develop, computationally apply, and experimentally validate electronic structure methods for all materials, with a focus on the complex materials, especially layered and two-dimensional materials, strongly-correlated materials, and liquid water. This was achieved by over 200 published journal articles authored by about 17 senior investigators from physics and chemistry and from theory, computation, and experiment, plus their collaborators. In particular, the Centers confirmed the predictive power of the SCAN (strongly constrained and appropriately normed) density functional, which was constructed to satisfy 17 known exact constraints and several appropriate norms. Without being fitted to real bonded systems, and at a modest computational cost, SCAN correctly predicted covalent, ionic, metallic, hydrogen, and van der Waals bonds in many challenging materials. SCAN gave an improved description of defects in semiconductors, surface properties of metals, seven phases of ice, liquid water, liquid and supercooled silicon, subtle structural distortions in ferroelectrics, formation energies and structural predictions for solids, and critical pressures for structural phase transitions. Perhaps most remarkably, SCAN correctly described some strongly-correlated materials that were previously believed to be beyond the reach of density-functional approximations. SCAN is the only density functional that correctly predicts the band gap closing under chemical doping of the cuprate high-temperature superconducting materials. SCAN also predicts a landscape of competing stripe and magnetic phases in the cuprates. For some materials with some codes, SCAN has convergence problems that are greatly reduced by the CCM-developed r 2 SCAN, without loss of accuracy or rigor. SCAN and r 2 SCAN still make some self-interaction error, which is greatly reduced by the CCDM/ CCM-developed local orbital scaling correction (LOSC). These Centers further proved that the fundamental energy gaps of a solid from an orbital energy difference and from total energy differences are the same for a large class of generalized Kohn-Sham (GKS) functionals, including SCAN and standard hybrid functionals, and that symmetry breaking arises when a dynamic density fluctuation drops to zero frequency. The Centers identified new mechanisms for catalysis in layered materials with ions intercalated between the layers, investigated charge density waves both in model systems and in real layered materials, studied changes of band gap with the number of layers, and explored topological ultrathin films, bent nanoribbons, and defects.

08 HYDROGEN↗