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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 181 records · Page 10
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DOE OSTI2023

Revealing quasi-excitations in the low-density homogeneous electron gas with model exchange–correlation kernels

Time-dependent density functional theory within the linear response regime provides a solid mathematical framework to capture excitations. The accuracy of the theory, however, largely depends on the approximations for the exchange–correlation (xc) kernels. Away from the long-wavelength (or q = 0 short wave-vector) and zero-frequency (ω = 0) limit, the correlation contribution to the kernel becomes more relevant and dominant over exchange. The dielectric function, in principle, can encompass xc effects relevant to describe low-density physics. Furthermore, besides collective plasmon excitations, the dielectric function can reveal collective electron–hole excitations, often dubbed “ghost excitons.” Besides collective excitons, the physics of the low-density regime is rich, as exemplified by a static charge-density wave that was recently found for r s > 69, and was shown to be associated with softening of the plasmon mode. These excitations are seen to be present in much higher density 2D homogeneous electron gases of r s ≳ 4. Here, in this work, we perform a thorough analysis with xc model kernels for excitations of various nature. The uniform electron gas, as a useful model of real metallic systems, is used as a platform for our analysis. We highlight the relevance of exact constraints as we display and explain screening and excitations in the low-density region.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Analysis and visualization of energy densities. II. Insights from linear-response time-dependent density functional theory calculations

Inspired by the analysis of Kohn–Sham energy densities by Nakai and coworkers, we extended the energy density analysis to linear-response time-dependent density functional theory (LR-TDDFT) calculations. Using ethylene–tetrafluoroethylene and oxyluciferin–water complexes as examples, distinctive distribution patterns were demonstrated for the excitation energy densities of local excitations (within a molecular fragment) and charge-transfer excitations (between molecular fragments). It also provided a simple way to compute the effective energy of both hot carriers (particle and hole) from charge-transfer excitations via an integration of the excitation energy density over the donor and acceptor grid points.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Investigation of the Failure of Marcus Theory for Hydrated Electron Reactions

Reactions of the hydrated electron with a wide variety of substrates have been found to exhibit unusually similar activation energies in a manner incompatible with Marcus electron transfer theory. Given the fundamental linear response assumption of Marcus theory, one possible explanation for this apparent failure is that the underlying free energy surfaces governing the reactions are not harmonic, i.e., hydrated electron structural fluctuations exhibit non-Gaussian behavior. In this work, we test this hypothesis by using simulations to calculate the hydrated electron vertical detachment energy distribution. Furthermore, we consider both cavity and non-cavity models for the hydrated electron, between which the actual hydrated electron behavior is expected to lie. Our results identify a possible origin for non-Gaussian behavior of the hydrated electron, but show that it is not of sufficient magnitude to explain the failure of Marcus theory to describe its reactions. Thus, other explanations must be sought.

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

Graph-based quantum response theory and shadow Born–Oppenheimer molecular dynamics

Graph-based linear scaling electronic structure theory for quantum-mechanical molecular dynamics simulations [A. M. N. Niklasson et al., J. Chem. Phys. 144, 234101 (2016)] is adapted to the most recent shadow potential formulations of extended Lagrangian Born–Oppenheimer molecular dynamics, including fractional molecular-orbital occupation numbers [A. M. N. Niklasson, J. Chem. Phys. 152, 104103 (2020) and A. M. N. Niklasson, Eur. Phys. J. B 94, 164 (2021)], which enables stable simulations of sensitive complex chemical systems with unsteady charge solutions. The proposed formulation includes a preconditioned Krylov subspace approximation for the integration of the extended electronic degrees of freedom, which requires quantum response calculations for electronic states with fractional occupation numbers. For the response calculations, we introduce a graph-based canonical quantum perturbation theory that can be performed with the same natural parallelism and linear scaling complexity as the graph-based electronic structure calculations for the unperturbed ground state. Further, the proposed techniques are particularly well-suited for semi-empirical electronic structure theory, and the methods are demonstrated using self-consistent charge density-functional tight-binding theory both for the acceleration of self-consistent field calculations and for quantum-mechanical molecular dynamics simulations. Graph-based techniques combined with the semi-empirical theory enable stable simulations of large, complex chemical systems, including tens-of-thousands of atoms.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Evolution of coupled weakly driven waves in a dissipative plasma

The nonlinear collisional dynamics of coupled driven plasma waves in the presence of background dissipation is studied analytically within kinetic theory. Sufficiently near marginal stability, phase space correlations are poorly preserved and time delays become unimportant. The system is then shown to be governed by two first-order coupled autonomous differential equations of cubic order for the wave amplitudes and two complementary first-order equations for the evolution of their phases. That system of equations can be decoupled and further simplified to a single second-order differential equation of Liénard's type for each amplitude. Numerical solutions for this equation are obtained in the general case, while analytic solutions are obtained for special cases in terms of parameters related to the spacing of the resonances of the two waves in frequency space, e.g., wave lengths and oscillation frequencies. These parameters are further analyzed to find classes of quasi-steady saturation and pulsating scenarios. To classify equilibrium points, local stability analysis is applied, and bifurcation conditions are determined. When the two waves saturate at similar amplitude levels, their combined signal is shown to invariably exhibit amplitude beating and phase jumps of nearly π. In conclusion, the obtained analytical results can be used to benchmark simulations and to interpret eigenmode amplitude measurements in fusion experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Linear-scaling quadruple excitations in local pair natural orbital coupled-cluster theory

Here, we present a fast, asymptotically linear-scaling implementation of the perturbative quadruples energy correction in coupled-cluster theory using local natural orbitals. Our work follows the domain-based local pair natural orbital (DLPNO) approach previously applied to lower levels of excitations in coupled-cluster theory. Our DLPNO-CCSDT(Q) algorithm uses converged doubles and triples amplitudes from a preceding DLPNO-CCSDT computation to compute the quadruples amplitude and energy in the quadruples natural orbital (QNO) basis. We demonstrate the compactness of the QNO space, showing that more than 95% of the (Q) correction can be recovered using relatively loose natural orbital cutoffs, compared to the tighter cutoffs used in pair and triples natural orbitals at lower levels of coupled-cluster theory. We also highlight the accuracy of our algorithm in the computation of relative energies, which yields deviations of sub-kJ mol −1 in relative energy compared to the canonical CCSDT(Q). Timings are conducted on a series of growing linear alkanes (up to 10 carbons and 608 basis functions) and water clusters (up to 49 water molecules and 2842 basis functions) to establish the asymptotic linear-scaling of our DLPNO-(Q) algorithm.

Auxiliary functions↗
DOE OSTI2021

Self-Assembly of Flexible Linear–Semiflexible Bottlebrush–Flexible Linear Triblock Copolymers

Block copolymer (BCP) self-assembly is a fundamental process in which incompatible blocks spontaneously form organized microstructures with broad practical applications. Classical understanding is that the domain spacing is limited by the contour length of the polymer backbone. Here, using a combination of molecular design, chemical synthesis, small-/wide-angle X-ray scattering, transmission electron microscopy, and electron tomography, we discover that this molecular picture does not hold for architecturally semiflexible BCPs. For strongly segregated linear–semiflexible bottlebrush–linear triblock copolymers, the size of the bottlebrush domain can be twice the bottlebrush backbone contour length. The mechanism of such anomalous self-assembly is likely that the interfacial repulsion between the incompatible blocks is large enough to pull a part of the linear end blocks into the bottlebrush domain. This effectively increases the bottlebrush domain size. Moreover, the semiflexible bottlebrush widens the regime for the cylinder morphology that is associated with the volume fraction of the end blocks fC SFB ∈ (0.10, >0.41). This window is much wider than that for flexible linear BCPs, fC F ∈ (0.14, 0.35), and that predicted by the recent self-consistent field theory for linear-bottlebrush BCPs of the same chemistry and molecular architecture. Finally, our experimental findings reveal previously unrecognized mechanisms for the self-assembly of architecturally complex BCPs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Theoretical Investigations on the Plasmon-Mediated Dissociation of Small Molecules in the Presence of Silver Atomic Wires

Plasmonic nanoparticles can promote bond activation in adsorbed molecules under relatively benign conditions via excitation of the nanoparticle’s plasmon resonance. As the plasmon resonance often falls within the visible light region, plasmonic nanomaterials are a promising class of catalysts. However, the exact mechanisms through which plasmonic nanoparticles activate the bonds of nearby molecules are still unclear. Herein, we evaluate Ag 8 –X 2 (X = N, H) model systems via real-time time-dependent density functional theory (RT-TDDFT), linear response time-dependent density functional theory (LR-TDDFT), and Ehrenfest dynamics in order to better understand the bond activation processes of N 2 and H 2 facilitated by the presence of the atomic silver wire under excitation at the plasmon resonance energies. We find that dissociation is possible for both small molecules at high electric field strength. Activation of each adsorbate is symmetry- and electric field-dependent, and H 2 activates at lower electric field strengths than N 2 . Furthermore, this work serves as a step toward understanding the complex time-dependent electron and electron–nuclear dynamics between plasmonic nanowires and adsorbed small molecules.

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

Hilbert series, the Higgs mechanism, and HEFT

We expand Hilbert series technologies in effective field theory for the inclusion of massive particles, enabling, among other things, the enumeration of operator bases for non-linearly realized gauge theories. We find that the Higgs mechanism is manifest at the level of the Hilbert series, as expected for the partition function of an S-matrix that is subject to the Goldstone equivalence theorem. In addition to massive vectors, we detail how other massive, spinning particles can be studied with Hilbert series; in particular, we spell out the ingredients for massive gravity in general spacetime dimensions. Further methodology is introduced to enable Hilbert series to capture the effect of spurion fields acquiring vevs. We apply the techniques to the Higgs Effective Field Theory (HEFT), providing a systematic enumeration of its operator basis. This is achieved both from a direct and a custodial symmetry spurion-based approach; we compare and contrast the two approaches, and our results to those appearing in previous literature.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Linear-Scaling Local Natural Orbital-Based Full Triples Treatment in Coupled-Cluster Theory

We present an efficient, asymptotically linear-scaling implementation of the canonically O(N 8 ) coupled-cluster method with singles, doubles, and full triples excitations (CCSDT) method. We apply the domain-based local pair natural orbital (DLPNO) approach for computing CCSDT amplitudes. Our method, called DLPNO–CCSDT, uses the converged coupled-cluster amplitudes from a preceding DLPNO–CCSD(T) computation as a starting point for the solution of the CCSDT equations in the local natural orbital basis. To simplify the working equations, we t1-dress our two-electron integrals and Fock matrices, allowing our equations to take on the form of CCDT. With appropriate parameters, our method can recover more than 99.99% of the total canonical CCSDT correlation energy. In addition, we demonstrate that our method consistently yields sub-kJ mol –1 errors in relative energies when compared to canonical CCSDT, and, likewise, when computing the difference between CCSDT and CCSD(T). Finally, to highlight the low scaling of our algorithm, we present timings on linear alkanes (up to 30 carbons and 730 basis functions) and water clusters (up to 131 water molecules and 3144 basis functions).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nonlinear Sigma model amplitudes to all loop orders are contained in the Tr ( Φ 3 ) theory

Scattering amplitudes for the simplest theory of colored scalar particles—the Tr ( Φ 3 ) theory—have recently been the subject of active investigations. In this work we describe an unanticipated wider implication of this work: the Tr ( Φ 3 ) theory secretly contains nonlinear sigma model (NLSM) amplitudes to all loop orders. The NLSM amplitudes are obtained from Tr ( Φ 3 ) amplitudes by a unique shift of kinematic variables. We show that this shifted kinematics produces amplitudes for a cubic theory with a linear term in the potential, with extrema spontaneously breaking U ( N ) → U ( N − k ) × U ( k ) . The Goldstone amplitudes for this theory coincide with those of pions in the U ( N ) × U ( N ) → U ( N ) chiral Lagrangian to all orders in the planar limit. We also give a purely on-shell understanding of this correspondence, showing that integrands defined by the kinematic shifts have the correct residues on poles and appropriately produce the Adler zero. Finally, we discuss how similar kinematic shifts produce certain infinite classes of mixed amplitudes of pions and Tr ( Φ 3 ) scalars, most of which are not interpretable from the Lagrangian description. Published by the American Physical Society 2024

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Statistical Study of the Nonthermal Continuum Radiation Beaming Angle Measured by the High Frequency Receiver on Van Allen Probes-A

The nonthermal continuum (NTC) radiation beaming angle is computed over the entire Van Allen Probes-A mission when the spacecraft was in the dawn sector. The conditions in the dawn sector are favorable for the wave vector to lie near/in the spacecraft's spin plane allowing a favorable estimate of the beaming angle, and the dawn sector is also advantageous in that previous studies show NTC occurrence to peak in this sector. We found that scatter plots, over the entire mission, of beaming angle versus magnetic latitude form a distinct inverted-V pattern, with the apex at/near the magnetic equator. This pattern was sharpest for frequencies ( f ) ≲ 100 kHz. Using the NTC beaming formula from the linear mode conversion theory (LMCT), we show that such an inverted-V pattern is expected due to the large variation in the plasmapause location over the entire mission. The theoretical derived pattern qualitatively reproduces the observed pattern but not quantitatively. The lack of quantitative agreement is discussed and is attributed to several factors, one factor is off-centered emissions from the radio window. The qualitative agreement strongly supports LMCT as being the dominant mechanism generating NTC for f ≲ 100 kHz. For f ≳ 100 kHz, the inverted-V pattern becomes less distinct, and strong near-equatorial beaming is observed. Finally, after considering contamination of our selections by left-handed polarized AKR, our study suggests that besides LMCT another unidentified NTC generation mechanism becomes important for f ≳ 100 kHz.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Coupled cluster theory on modern heterogeneous supercomputers

This study examines the computational challenges in elucidating intricate chemical systems, particularly through ab-initio methodologies. This work highlights the Divide-Expand-Consolidate (DEC) approach for coupled cluster (CC) theory—a linear-scaling, massively parallel framework—as a viable solution. Detailed scrutiny of the DEC framework reveals its extensive applicability for large chemical systems, yet it also acknowledges inherent limitations. To mitigate these constraints, the cluster perturbation theory is presented as an effective remedy. Attention is then directed towards the CPS (D-3) model, explicitly derived from a CC singles parent and a doubles auxiliary excitation space, for computing excitation energies. The reviewed new algorithms for the CPS (D-3) method efficiently capitalize on multiple nodes and graphical processing units, expediting heavy tensor contractions. As a result, CPS (D-3) emerges as a scalable, rapid, and precise solution for computing molecular properties in large molecular systems, marking it an efficient contender to conventional CC models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗