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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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We studied the electron dynamic correlation using inelastic X-ray scattering measurements. The data files contain a 2D array of numeric data that is used to produce the figures in the paper, "Observation of Real-space Dynamic Electron Correlation in Beryllium."
The rapidly expanding field of polaritonic chemistry requires accurate theoretical simulations to understand new phenomena at the atomic scale. Computing the optoelectronic properties of molecules using established electronic structure methods is a careful balance of accuracy and computational expense, and expanding these methods to quantum electrodynamics to describe coupled cavity-molecule systems is an active topic of development. Key to these methods are the Hamiltonian operators representing the photon cavity modes. The recently introduced quantum electrodynamics time-dependent configuration interaction (QED-TDCI) method allows for the combination of electron dynamics simulations with quantum electrodynamics, enabling the simulation of time-dependent optoelectronic properties of cavity-molecule systems. Using this method, a comparison of two many-state QED Hamiltonians—the Pauli-Fierz and quantum Rabi model Hamiltonians—is presented, with a particular focus on time-dependent properties in applied electric fields.
The explicit real-time propagation approach for time-dependent density functional theory (RT-TDDFT) has increasingly become a popular first-principles computational method for modeling various time-dependent electronic properties of complex chemical systems. Here, in this Perspective, we provide a nontechnical discussion of how this first-principles simulation approach has been used to gain novel physical insights into nonequilibrium electron dynamics phenomena in recent years. Following a concise overview of the RT-TDDFT methodology from a practical standpoint, we discuss our recent studies on the electronic stopping of DNA in water and the Floquet topological phase as examples. Our discussion focuses on how RT-TDDFT simulations played a unique role in deriving new scientific understandings. We then discuss existing challenges and some new advances at the frontier of RT-TDDFT method development for studying increasingly complex dynamic phenomena and systems.
One of the central challenges in condensed matter physics is to comprehend systems that have strong disorder and strong interactions. In the strongly localized regime, their subtle competition leads to glassy electron dynamics which ceases to exist well before the insulator-to-metal transition is approached as a function of doping. Here, we report on the discovery of glassy electron dynamics deep inside the good metal regime of an electron-doped quantum paraelectric system: KTaO 3 . We reveal that upon excitation of electrons from defect states to the conduction band, the excess injected carriers in the conduction band relax in a stretched exponential manner with a large relaxation time, and the system evinces simple aging phenomena—a telltale sign of glassy dynamics. Most significantly, we observe a critical slowing down of carrier dynamics below 35 K, concomitant with the onset of quantum paraelectricity in the undoped KTaO 3 . Our combined investigation using second harmonic generation technique, density functional theory and phenomenological modeling demonstrates quantum fluctuation-stabilized soft polar modes as the impetus for the glassy behavior. This study addresses one of the most fundamental questions regarding the potential promotion of glassiness by quantum fluctuations and opens a route for exploring glassy dynamics of electrons in a well-delocalized regime.
A large set of neptunium compounds with different oxidation states (III to VII) was assembled to study the Mössbauer isomer shift by wave function calculations and better understand covalency in f-elements complexes. The contact density approach was used to calculate the isomer shift using complete active space self-consistent field (CASSCF) multiconfiguration wave functions, as well as matrix product states [from Density Matrix Renormalization Group (DMRG) algorithms] for large active spaces. Dynamic correlation effects for the isomer shifts were treated via CASPT2 energy derivatives with respect to the nuclear radius. The CASSCF calculations appear to produce different orbital overlocalization errors for low and high Np oxidation states. For compounds with low Np oxidation numbers, the errors can be attributed to the overlocalization of the 5f orbitals. For the compounds with high Np oxidation numbers, the main errors arise from an overlocalization of ligand orbitals and concomitant to weak donation bonding. Attempts to mitigate the overlocalization errors with large active spaces using DMRG were only partially successful, showing that explicit treatment of dynamic correlation is necessary for accurate predictions of Mössbauer isomer shifts. The CASPT2 calculations perform very satisfactorily. For a subset of Np compounds, both static and dynamic correlation effects were substantial. Furthermore, a rational active space selection based on orbital entanglement diagrams proved beneficial for determining the optimal reference wave function.
Explicit time-dependent electronic structure theory methods are increasingly prevalent in the areas of condensed matter physics and quantum chemistry, with the broad-band optical absorptivity of molecular and small condensed-phase systems nowadays routinely studied with such approaches. Here, in this paper, it is demonstrated that electronic dynamics simulations can similarly be employed to study cross sections for the scattering-induced electronic excitations probed in nonresonant inelastic X-ray scattering and momentum-resolved electron energy loss spectroscopies. A method is put forth for evaluating the electronic dynamic structure factor, which involves the application of a momentum boost-type perturbation and transformation of the resulting reciprocal space density fluctuations into the frequency domain. Good agreement is first demonstrated between the dynamic structure factor extracted from these electronic dynamics simulations and the corresponding transition matrix elements from linear response theory. The method is then applied to some extended (quasi)one-dimensional systems, for which the wave vector becomes a good quantum number in the thermodynamic limit. Finally, the dispersion of many-body excitations in a series of hydrogen-terminated graphene flakes (and twisted bilayers thereof) is investigated to highlight the utility of the presented approach for capturing morphology-dependent effects in the inelastic scattering cross sections of nanostructured and/or noncrystalline materials.
Microscopes utilizing convergent electron and ion beams are emerging as powerful tools for both imaging and manipulating two-dimensional materials with atomic resolution, allowing the ultimate limits of nanofabrication to be realized. In this chapter, we detail the use of time-dependent electronic structure theory to determine the excited state properties and reactivity of functionalized graphene nanostructures. A time-dependent density functional theory treatment of electronic excitations of materials is presented, with specific emphasis on predicting the position-dependent electronic response of two-dimensional nanomaterials to electron beams. The method is demonstrated in a study highlighting the important role that electronic excitation can play in opening reaction pathways relevant to atomically precise defect manipulation in graphene. Finally, we provide some perspective on future development directions for methods of simulating nonequilibrium electronic and vibrational dynamics induced by electron/ion beams.
Dynamical electron correlation has a major impact on the computed values of molecular properties and the energetics of molecular processes. This study focused on the effect of dynamical electron correlation on the spectroscopic constants ($R$ e , $ω$ e , $D$ e ), and potential energy curves, Δ$E$($R$), of the covalently bound AH and AF molecules, A = B–F. The changes in the spectroscopic constants (Δ$R$ e , Δ$ω$ e , Δ$D$ e ) caused by dynamical correlation are erratic and, at times, even surprising. These changes can be understood based on the dependence of the dynamical electron correlation energies of the AH and AF molecules as a function of the bond distance, i.e., Δ$E$ DEC ($R$). At large $R$, the magnitude of Δ$E$ DEC ($R$) increases nearly exponentially with decreasing $R$, but this increase slows as $R$ continues to decrease and, in many cases, even reverses at very short $R$. The changes in Δ$E$ DEC ($R$) in the region around $R$ e were as unexpected as they were surprising, e.g., distinct minima and maxima were found in the curves of Δ$E$ DEC ($R$) for the most polar molecules. The variations in Δ$E$ DEC ($R$) for $R$ ≲ $R$ e are directly correlated with major changes in the electronic structure of the molecules as revealed by a detailed analysis of the spin-coupled generalized valence bond wave function. In conclusion, the results reported here indicate that we have much to learn about the nature of dynamical electron correlation and its effect on chemical bonds and molecular properties and processes.
Electron dynamics in external electric fields governs the behavior of solid-state electronic devices. First-principles calculations enable precise predictions of charge transport in low electric fields. However, studies of high-field electron dynamics remain elusive due to a lack of accurate and broadly applicable methods. In this work, we develop an efficient approach to solve the real-time Boltzmann transport equation with both the electric field term and ab initio electron-phonon collisions. These simulations provide field-dependent electronic distributions in the time domain, allowing us to investigate both transient and steady-state transport in electric fields ranging from low to high (> 10 kV/cm). The broad capabilities of our approach are shown by computing nonequilibrium electron occupations and velocity-field curves in Si, GaAs, and graphene, obtaining results in quantitative agreement with experiment. Our approach sheds light on microscopic details of transport in high electric fields, including the dominant scattering mechanisms and valley occupation dynamics. Our results demonstrate quantitatively accurate calculations of electron dynamics in low to high electric fields, with broad application to power and micro-electronics, optoelectronics, and sensing.
This paper describes an empirical study of the basic mechanisms by which electrons precipitate from the geomagnetic field to produce 'auroral X rays' during periods of geomagnetic activity. The study was based on data obtained by the Echo satellites. Echo I, launched in 1970, injected 40 keV, 0.1 amp electron pulses at low latitude (L ? 2.6) and successfully measured the returning pulses from the conjugate region. Electric fields and multiple Coulomb scattering were studied. Echo II, launched in 1972 from high latitude (L ? 8) studied the interaction of the beams with background radiation and the detailed motion of the beams near the rocket. Evidence for a beam plasma instability was obtained. Echo III launched in April 1974, (L ? 5.5) detected a series of conjugate echoes during the presence of a strong convective field in the magnetosphere. It was shown that the electric field measurement in the ionosphere using the incoherent backscatter radar and detectors on the rocket was transferred to the equatorial plane as though field lines were equipotentials.
The Electron Echo experiments are described which were conducted with three sounding rockets to study the basic mechanisms by which electrons precipitate from the geomagnetic field to produce auroral X-rays during periods of geomagnetic activity. Echo I (1970) injected electron pulses at low latitude and successfully measured the returning pulses from the conjugate region. Echo II (1972) was launched from high latitude, studied the interaction of electron beams with background radiation as well as beam motion near the rocket, and obtained evidence for a beam plasma instability. Echo III (1974) detected a series of conjugate echoes during the presence of a strong convective field in the magnetosphere and conducted an unsuccessful search for beam bunching at the local plasma frequency. It is shown that the electric field measurement in the ionosphere, using incoherent backscatter radar and detectors on the rocket, was transferred to the equatorial plane as though field lines were equipotentials.
We extended our studies of the effect of dynamical electron correlation on the covalent bonds in the AH and AF series (A = B–F) to the recoupled pair bonds in the excited $a$ 4 Σ - states of the CH and CF molecules. Dynamical correlation is energetically less important in the $a$ 4 Σ - states than in the corresponding X 2 Π states for both molecules, which is reflected in smaller changes in bond energies ($D$ e ). Changes in the equilibrium bond distance ($R$ e ) and vibrational frequency ($ω$ e ), on the other hand, are influenced by the changes in the slope and curvature of the dynamical electron correlation energy as a function of the internuclear distance $R$, $E$ DEC ($R$). In the CH($a$ 4 Σ - ) state, these changes are much smaller than in the CH(X 2 Π) state, but in the CF($a$ 4 Σ - ) state, they are larger, reflecting a significant difference in the shapes of $E$ DEC ($R$) curves. At large $R$, the shape of $E$ DEC ($R$) curves for covalent and recoupled pair bonds is similar although different in magnitude. For the CH($a$ 4 Σ - ) state, $E$ DEC ($R$) has a minimum at $R$ = $R$ e + 0.72 Å as the orbitals associated with the formation of the recoupled pair bond switch places. $E$ DEC (R) for the CF($a$ 4 Σ - ) state decreases continuously throughout the bound region of the potential energy curve because the dynamical correlation energy associated with the electrons in the lone pair orbitals is increasing. In conclusion, these results support our earlier conclusion that we still have much to learn about the nature of dynamical electron correlation in molecules.
The relaxation dynamics of hot electrons in the X6 and X7 satellite and upper conduction bands in GaP was directly measured by femtosecond UV-pump-IR-probe absorption spectroscopy. From a fit to the induced IR-absorption spectra the dominant scattering mechanism giving rise to the absorption at early delay times was determined to be intervalley scattering of electrons out of the X7 upper conduction-band valley. For long delay times the dominant scattering mechanism is electron-hole scattering. Electron transport dynamics of the upper conduction band of GaP has been time resolved.
Two different approaches have been implemented to include the effect of dynamic electron correlation in the Non-Orthogonal Configuration Interaction for Fragments (NOCI-F) method. The first is based on shifting the diagonal matrix elements of the NOCI matrix, while the second incorporates the dynamic correlation explicitly in the fragment wave functions used to construct the many-electron basis functions of the NOCI. The two approaches are illustrated for the calculation of the electronic coupling relevant in singlet fission and the coupling of spin moments in organic radicals. Comparison of the calculated diabatic couplings, the NOCI energies and wave functions shows that dynamic electron correlation is not only efficiently but also effectively incorporated by the shifting approach and can largely affect the coupling between electronic states. Additionally, it brings the NOCI coupling of the spin moments in close agreement with benchmark calculations.
In this study, we consider the problem of learning density-dependent molecular Hamiltonian matrices from time series of electron density matrices, all in the context of Hartree–Fock theory. Prior work developed a solution to this problem for small molecular systems with density and Hamiltonian matrices of size at most 6 × 6. Here, using a battery of techniques, we scale prior methods to larger molecular systems with, for example, 29 × 29 matrices. This includes systems that either have more electrons or are expressed in large basis sets such as 6-311++G**. Scaling the method to larger systems enhances its relevance for realistic applications in chemistry and physics. To achieve this scaling, we apply dimensionality reduction, ridge regression and analytic computation of Hessians. Through the combination of these techniques, we are able to learn Hamiltonians by minimizing an objective function that encodes local propagation error. Importantly, these learned Hamiltonians can then be used to predict electron dynamics for thousands of steps: When we use our learned Hamiltonians to numerically solve the time-dependent Hartree–Fock equation, we obtain predicted dynamics that are in close quantitative agreement with ground truth dynamics. This includes field-off trajectories similar to the training data and field-on trajectories outside of the training data.
Here, we investigate the ultrafast electron dynamics triggered by terahertz and optical pulses in thin platinum and gold films by probing their transient optical reflectivity. The response of the platinum film to an intense terahertz pulse is similar to the optically induced one and can be described by a two-temperature model with a 20% larger electron–phonon coupling for the terahertz-driven dynamics compared to the optically induced one, ascribed to an additional nonthermal electron–phonon coupling contribution. Surprisingly, gold films exhibit a much smaller terahertz pulse-induced reflectivity change and with a sign opposite to the optical case. Additionally we explain this remarkable observation with field emission of electrons due to Fowler–Nordheim tunneling, enabled in samples with thicknesses below the structural percolation threshold, where nanostructuring promotes near-field enhancement. Our results provide a fundamental insight into the ultrafast processes relevant to modern electro- and magneto-optical applications.