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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Potential energy surfaces for high-energy N + O 2 collisions

Potential energy surfaces for high-energy collisions between an oxygen molecule and a nitrogen atom are useful for modeling chemical dynamics in shock waves. In the present work, we present doublet, quartet, and sextet potential energy surfaces that are suitable for studying collisions of O 2 ( 3 Σ$^{–}_{g}$) with N( 4 S) in the electronically adiabatic approximation. Two sets of surfaces are developed, one using neural networks (NNs) with permutationally invariant polynomials (PIPs) and one with the least-squares many-body (MB) method, where a two-body part is an accurate diatomic potential and the three-body part is expressed with connected PIPs in mixed-exponential-Gaussian bond order variables (MEGs). We find, using the same dataset for both fits, that the fitting performance of the PIP-NN method is significantly better than that of the MB-PIP-MEG method, even though the MB-PIP-MEG fit uses a higher-order PIP than those used in previous MB-PIP-MEG fits of related systems (such as N 4 and N 2 O 2 ). However, the evaluation of the PIP-NN fit in trajectory calculations requires about 5 times more computer time than is required for the MB-PIP-MEG fit.

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

Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with the Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas Phase and Solvents Ranging from Hexanes to Acetonitrile

Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). We analyze the performance of polarizable continuum solvation models available in Q-Chem that partition the solvent response into fast and slow time scales, and clear trends emerge when measurements corresponding to the four small 4-(dimethylamino)benzonitrile (DMABN)-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the well-separated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by the linear-response time-dependent density functional theory within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Density Functional Extension to Excited-State Mean-Field Theory

Here, we investigate an extension of excited-state mean-field theory in which the energy expression is augmented with density functional components in an effort to include the effects of weak electron correlations. The approach remains variational and entirely time independent, allowing it to avoid some of the difficulties associated with linear response and the adiabatic approximation. In particular, all of the electrons' orbitals are relaxed state specifically, and there is no reliance on Kohn-Sham orbital energy differences, both of which are important features in the context of charge transfer. Preliminary testing shows clear advantages for single-component charge transfer states, but the method, at least in its current form, is less reliable for states in which multiple particle-hole transitions contribute significantly.

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

Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory

While time-dependent density functional theory has emerged as a method of choice for computing electronic spectra and response of molecules and materials, its reliability is hindered by the adiabatic approximation that is commonly made. In this work, we address one problematic aspect that arises from this approximation: an incorrect pole structure in the quadratic response function, leading to unphysical divergences in excited state-to-state transition probabilities and hyperpolarizabilties. We find the form of the exact quadratic response kernel and derive a practical and accurate approximation that cures the divergence. Here, we demonstrate our results on excited state-to-state transition probabilities of a model system and of the LiH molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Accurate double excitations from ensemble density functional calculations

The recent use of a new ensemble in density functional theory (DFT) to produce direct corrections to the Kohn-Sham transitions yields the elusive double excitations that are missed by time-dependent DFT (TDDFT) with the standard adiabatic approximation. But accuracies are lower than for single excitations, and formal arguments about TDDFT suggest that a correction kernel is needed. In principle, ensemble DFT with direct corrections at the exchange level must yield accurate doubles in the weakly correlated limit. We illustrate with exact calculations and analytic results on the Hubbard dimer. Lastly, we also explain the error in formal arguments in TDDFT.

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

Valence shell photoelectron angular distributions and vibrationally resolved spectra of imidazole: A combined experimental–theoretical study

Linearly polarized synchrotron radiation has been used to record polarization dependent valence shell photoelectron spectra of imidazole in the photon energy range 21–100 eV. These have allowed the photoelectron angular distributions, as characterized by the anisotropy parameter β, and the electronic state intensity branching ratios to be determined. Complementing these experimental data, theoretical photoionization partial cross sections and β-parameters have been calculated for the outer valence shell orbitals. The assignment of the structure appearing in the experimental photoelectron spectra has been guided by vertical ionization energies and spectral intensities calculated by various theoretical methods that incorporate electron correlation and orbital relaxation. Strong orbital relaxation effects have been found for the 15a', nitrogen lone-pair orbital. The calculations also predict that configuration mixing leads to the formation of several low-lying satellite states. The vibrational structure associated with ionization out of a particular orbital has been simulated within the Franck–Condon model using harmonic vibrational modes. The adiabatic approximation appears to be valid for the X 2A" state, with the β-parameter for this state being independent of the level of vibrational excitation. However, for all the other outer valence ionic states, a disparity occurs between the observed and the simulated vibrational structure, and the measured β-parameters are at variance with the behavior expected at the level of the Franck–Condon approximation. Furthermore, these inconsistencies suggest that the excited electronic states may be interacting vibronically such that the nuclear dynamics occur over coupled potential energy surfaces.

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

Size-dependent errors in real-time electron density propagation

Real-time (RT) electron density propagation with time-dependent density functional theory (TDDFT) or Hartree–Fock (TDHF) is one of the most popular methods to model the charge transfer in molecules and materials. However, both RT-TDHF and RT-TDDFT within the adiabatic approximation are known to produce inaccurate evolution of the electron density away from the ground state in model systems, leading to large errors in charge transfer and erroneous shifting of peaks in absorption spectra. Given the poor performance of these methods with small model systems and the widespread use of the methods with larger molecular and material systems, here we bridge the gap in our understanding of these methods and examine the size-dependence of errors in RT density propagation. We analyze the performance of RT density propagation for systems of increasing size during the application of a continuous resonant field to induce Rabi-like oscillations, during charge-transfer dynamics, and for peak shifting in simulated absorption spectra. We find that the errors in the electron dynamics are indeed size dependent for these phenomena, with the largest system producing the results most aligned with those expected from linear response theory. The results suggest that although the RT-TDHF and RT-TDDFT methods may produce severe errors for model systems, the errors in charge transfer and resonantly driven electron dynamics may be much less significant for more realistic, large-scale molecules and materials.

Chemistry↗
DOE OSTI2013

THEORETICAL ESTIMATES OF STELLAR e {sup -} CAPTURES. I. THE HALF-LIFE OF {sup 7}Be IN EVOLVED STARS

The enrichment of Li in the universe is still unexplained, presenting various puzzles to astrophysics. One open issue is that of obtaining reliable estimates for the rate of e {sup -} captures on {sup 7}Be for T and {rho} conditions that are different from the solar ones. This is of crucial importance for modeling the Galactic nucleosynthesis of Li. In this framework, we present here a new theoretical method for calculating the e {sup -} capture rate in typical conditions for evolved stars. Furthermore, we show how our approach compares with state-of-the-art techniques for solar conditions, where various estimates are available. Our computations include (1) 'traditional' calculations of the electronic density at the nucleus, to which the e {sup -} capture rate for {sup 7}Be is proportional, for different theoretical approaches including the Thomas-Fermi, Poisson-Boltzmann, and Debye-Hueckel (DH) models of screening; and (2) a new computation, based on a formalism that goes beyond the previous ones, adopting a mean-field 'adiabatic' approximation to the scattering process. The results obtained with the new approach as well as with traditional ones and their differences are discussed in some detail, starting from solar conditions, where our approach and the DH model essentially converge to the same solution. We then analyze the applicability of both our method and the DH model to a rather broad range of T and {rho} values, embracing those typical of red giant stars, where both bound and continuum states contribute to the capture. We find that over a wide region of the parameter space explored, the DH approximation does not really stand, so that the more general method we suggest should be preferred. As a first application, we briefly reanalyze the {sup 7}Li abundances in red giant branch and asymptotic giant branch stars of the Galactic disk in light of a revision in the Be decay only; however, we emphasize that the changes we find in the electron density at the nucleus would also induce effects on the electron screening (for p-captures on Li itself, as well as for other nuclei) so that our new approach might have rather wide astrophysical consequences.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Multiband effects in equations of motion of observables beyond the semiclassical approach

The equations of motion (EOM)for the position and gauge invariant crystal momentum are considered for multiband wave packets of Bloch electrons. For a localized packet in a subset of bands well-separated from the rest of the band structure of the crystal, one can construct an effective electromagnetic Hamiltonian with respect to the center of the packet. We show that the EOM can be obtained via a projected operator procedure, which is derived from the adiabatic approximation within perturbation theory. These relations explicitly contain information from each band captured in the expansion coefficients and energy band structure of the Bloch states as well as non-Abelian features originating from interband Berry phase properties. This general and transparent Hamiltonian-based approach is applied to a wave packet spread over a single band, a set of degenerate bands, and two linear crossing bands. The generalized EOM hold promise for novel effects in transport currents and Hall effect phenomena.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Synchronous acceleration with tapered dielectric-lined waveguides

Here, we present a general concept to accelerate non-relativistic charged particles. Our concept employs an adiabatically-tapered dielectric-lined waveguide which supports accelerating phase velocities for synchronous acceleration. We propose an ansatz for the transient field equations, show it satisfies Maxwell's equations under an adiabatic approximation and find excellent agreement with a finite-difference time-domain computer simulation. The fields were implemented into the particle-tracking program {\sc astra} and we present beam dynamics results for an accelerating field with a 1-mm-wavelength and peak electric field of 100~MV/m. The numerical simulations indicate that a $\sim 200$-keV electron beam can be accelerated to an energy of $\sim10$~MeV over $\sim 10$~cm. The novel scheme is also found to form electron beams with parameters of interest to a wide range of applications including, e.g., future advanced accelerators, and ultra-fast electron diffraction.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

Direct driving of electronic and phononic degrees of freedom in a honeycomb bilayer with infrared light

Here, we study theoretically AB-stacked honeycomb bilayers driven by light in resonance with an infrared phonon within a tight-binding description. We characterize the phonon properties of honeycomb bilayers with group theory and construct an electronic time-dependent tight-binding model for the system following photoexcitation in resonance with an infrared phonon. We adopt an atomically adiabatic approximation [V. Mohanty and E. J. Heller, Proc. Natl. Acad. Sci. 116, 18316 (2019)] to describe classically vibrating nuclei, but obtain the Floquet quasienergy spectrum associated with the time-dependent model exactly. We introduce a general scheme to disentangle the complex low-frequency Floquet spectrum to elucidate the relevant Floquet bands. As a prototypical example, we consider bilayer graphene. We find that light in the low-frequency regime can induce a band gap in the quasienergy spectrum in the vicinity of the $K$ points even if it is linearly polarized, in contrast with the expectations within the Born-Oppenheimer approximation and the high-frequency regime. Finally, we analyze the diabaticity of the driven electron and driven phonon processes and find contrasting effects on the autocorrelation functions at the same driving frequency: Driven phonons preserve the character of the initial state while driven electrons exhibit strong deviations within a few drive cycles. The procedure outlined here can be applied to other materials to describe the combined effects of low-frequency light on phonons and electrons.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Theory of inelastic multiphonon scattering and carrier capture by defects in semiconductors: Application to capture cross sections

Inelastic scattering and carrier capture by defects in semiconductors are the primary causes of hot-electron-mediated degradation of power devices, which holds up their commercial development. At the same time, carrier capture is a major issue in the performance of solar cells and light-emitting diodes. A theory of nonradiative (multiphonon) inelastic scattering by defects, however, is nonexistent, while the theory for carrier capture by defects has had a long and arduous history. As such, we report the construction of a comprehensive theory of inelastic scattering by defects, with carrier capture being a special case. We distinguish between capture under thermal equilibrium conditions and capture under nonequilibrium conditions, e.g., in the presence of an electrical current or hot carriers where carriers undergo scattering by defects and are described by a mean free path. In the thermal-equilibrium case, capture is mediated by a nonadiabatic perturbation Hamiltonian, originally identified by Huang and Rhys and by Kubo, which is equal to linear electron-phonon coupling to first order. In the nonequilibrium case, we demonstrate that the primary capture mechanism is within the Born-Oppenheimer approximation (adiabatic transitions), with coupling to the defect potential inducing Franck-Condon electronic transitions, followed by multiphonon dissipation of the transition energy, while the nonadiabatic terms are of secondary importance (they scale with the inverse of the mass of typical atoms in the defect complex). We report first-principles density-functional-theory calculations of the capture cross section for a prototype defect using the projector-augmented wave, which allows us to employ all-electron wave functions. We adopt a Monte Carlo scheme to sample multiphonon configurations and obtain converged results. The theory and the results represent a foundation upon which to build engineering-level models for hot-electron degradation of power devices and the performance of solar cells and light-emitting diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Spin-density fluctuations and the fluctuation-dissipation theorem in 3 d ferromagnetic metals

Spatial and time scales of spin-density fluctuations (SDFs) were analyzed in 3d ferromagnets using ab initio linear-response calculations of complete wave-vector and energy dependence of the dynamic spin susceptibility tensor. We demonstrate that SDFs are spread continuously over the entire Brillouin zone and while the majority of them reside within the 3d bandwidth, a significant amount comes from much higher energies. A validity of the adiabatic approximation in spin dynamics is discussed. The SDF spectrum is shown to have two main constituents: a minor low-energy spin-wave contribution and a much larger high-energy component from more localized excitations. Furthermore, using the fluctuation-dissipation theorem, the on-site spin correlator and the related effective fluctuating moment were properly evaluated and their universal dependence on the 3d band population is further discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Semiclassical dynamics of spin density waves

Here, we present a theoretical framework for equilibrium and nonequilibrium dynamical simulation of quantum states with spin-density-wave (SDW) order. Within a semiclassical adiabatic approximation that retains electron degrees of freedom, we demonstrate that the SDW order parameter obeys a generalized Landau-Lifshitz equation. With the aid of an enhanced kernel polynomial method, our linear-scaling quantum Landau-Lifshitz dynamics (QLLD) method enables dynamical SDW simulations with N ≃ 10 5 lattice sites. Our real-space formulation can be used to compute dynamical responses, such as the dynamical structure factor, of complex and even inhomogeneous SDW configurations at zero or finite temperatures. Applying the QLLD to study the relaxation of a noncoplanar topological SDW under the excitation of a short pulse, we further demonstrate the crucial role of spatial correlations and fluctuations in the SDW dynamics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Derivation of an optical potential for statically deformed rare-earth nuclei from a global spherical potential

The coupled-channel theory is a natural way of treating nonelastic channels, in particular those arising from collective excitations characterized by nuclear deformations. A proper treatment of such excitations is often essential to the accurate description of experimental nuclear-reaction data and to the prediction of a wide variety of scattering observables. Stimulated by recent work substantiating the near validity of the adiabatic approximation in coupled-channel calculations for scattering on statically deformed nuclei, we explore the possibility of generalizing a global spherical optical model potential (OMP) to make it usable in coupled-channel calculations on this class of nuclei. To do this, we have deformed the Koning-Delaroche global spherical potential for neutrons, coupling a sufficient number of states of the ground state band to ensure convergence. We present an extensive study of the effects of collective couplings and nuclear deformations on integrated cross sections as well as on angular distributions for neutron-induced reactions on statically deformed nuclei in the rare-earth region. We choose isotopes of three rare-earth elements (Gd, Ho, W), which are known to be nearly perfect rotors, to exemplify the results of the proposed method. Predictions from our model for total, elastic and inelastic cross sections, as well as for elastic and inelastic angular distributions, are in reasonable agreement with measured experimental data. In conclusion, these results suggest that the deformed Koning-Delaroche potential provides a useful regional neutron optical potential for the statically deformed rare earth nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2018

Density response from kinetic theory and time-dependent density-functional theory for matter under extreme conditions

The density linear response function for an inhomogeneous system of electrons in equilibrium with an array of fixed ions is considered. Two routes to its evaluation for extreme conditions (e.g., warm dense matter) are considered. The first is from a recently developed short-time kinetic equation; the second is from time-dependent density functional theory. The result from the latter approach agrees with that from kinetic theory in the “adiabatic approximation,” providing support and contextual clarity for each. Both provide a connection to the phenomenological Kubo-Greenwood method for calculating transport properties.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Probabilistic structure of the geodynamo

One of the most intriguing features of Earth's axial magnetic dipole field, well known from the geological record, is its occasional and unpredictable reversal of polarity. Understanding the phenomenon is rendered very difficult by the highly nonlinear nature of the underlying magnetohydrodynamic problem. Numerical simulations of the liquid outer core, where regeneration occurs, are only able to model conditions that are far from Earth-like. On the analytical front, the situation is not much better; basic calculations, such as relating the average rate of reversals to various core parameters, have apparently been intractable. Here, we present a framework for solving such problems. Starting with the magnetic induction equation, we show that by considering its sources to be stochastic processes with fairly general properties, we can derive a differential equation for the joint probability distribution of the dominant toroidal and poloidal modes. This can be simplified to a Fokker-Planck equation and, with the help of an adiabatic approximation, reduced even further to an equation for the dipole amplitude alone. From these equations various quantities related to the magnetic field, including the average reversal rate, field strength, and time to complete a reversal, can be computed as functions of a small number of numerical parameters. As a result, these parameters in turn can be computed from physical considerations or constrained by paleomagnetic, numerical, and experimental data.

58 GEOSCIENCES↗