SEARCH · Search NASA
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
The anisotropic charge carrier diffusion coupled to ferroelastic twin domains in methylammonium lead iodide opens possibilities for further optimization of perovskite solar cells and optoelectronic devices via strain engineering and heat treatments.
Strong electron correlation plays an important role in transition-metal and heavy-metal chemistry, magnetic molecules, bond breaking, biradicals, excited states, and many functional materials, but it provides a significant challenge for modern electronic structure theory. The treatment of strongly correlated systems usually requires a multireference method to adequately describe spin densities and near-degeneracy correlation. However, quantitative computation of dynamic correlation with multireference wave functions is often difficult or impractical. Multiconfiguration pair-density functional theory (MC-PDFT) provides a way to blend multiconfiguration wave function theory and density functional theory to quantitatively treat both near-degeneracy correlation and dynamic correlation in strongly correlated systems; it is more affordable than multireference perturbation theory, multireference configuration interaction, or multireference coupled cluster theory and more accurate for many properties than Kohn–Sham density functional theory. This perspective article provides a brief introduction to strongly correlated systems and previously reviewed progress on MC-PDFT followed by a discussion of several recent developments and applications of MC-PDFT and related methods, including localized-active-space MC-PDFT, generalized active-space MC-PDFT, density-matrix-renormalization-group MC-PDFT, hybrid MC-PDFT, multistate MC-PDFT, spin–orbit coupling, analytic gradients, and dipole moments. We also review the more recently introduced multiconfiguration nonclassical-energy functional theory (MC-NEFT), which is like MC-PDFT but allows for other ingredients in the nonclassical-energy functional. We discuss two new kinds of MC-NEFT methods, namely multiconfiguration density coherence functional theory and machine-learned functionals.
Specialized computational chemistry packages have permanently reshaped the landscape of chemical sciences by providing tools to support and guide the experimental effort and for prediction of chemical and materials properties. In this regard, a special role has been played by electronic structure packages where complex chemical and materials processes can be modeled using first-principle-driven methodologies. Over the last few decades, the rapid development of computing technologies and a tremendous increase in computational power has offered a unique chance to study complex chemical transformations using sophisticated and predictive many-body techniques to describe correlated behavior of electrons in molecular and condensed phase systems at different levels of theory. In enabling these simulations, a critical role has been played by novel parallel algorithms capable of taking advantage of computational resources to address polynomial scaling of electronic structure methods. NWChem was among the first electronic structure codes that focused on delivering scalable performance for electronic structure simulations. Herein, we briefly review the NWChem suite of computational codes including its history, design principles, parallel tools, current capabilities, outreach and outlook.
PySCF is a Python-based general-purpose electronic structure platform that supports first-principles simulations of molecules and solids as well as accelerates the development of new methodology and complex computational workflows. Here, we explain the design and philosophy behind PySCF that enables it to meet these twin objectives. With several case studies, we show how users can easily implement their own methods using PySCF as a development environment. We then summarize the capabilities of PySCF for molecular and solid-state simulations. Finally, we describe the growing ecosystem of projects that use PySCF across the domains of quantum chemistry, materials science, machine learning, and quantum information science.
We present a new geodesic-based method for geometry optimization in a basis set of redundant internal coordinates. Overall, our method updates the molecular geometry by following the geodesic generated by a displacement vector on the internal coordinate manifold, which dramatically reduces the number of steps required to converge to a minimum. Our method can be implemented in any existing optimization code, requiring only implementation of derivatives of the Wilson B-matrix and the ability to numerically solve an ordinary differential equation.
We review the GPAW open-source Python package for electronic structure calculations. GPAW is based on the projector-augmented wave method and can solve the self-consistent density functional theory (DFT) equations using three different wave-function representations, namely real-space grids, plane waves, and numerical atomic orbitals. The three representations are complementary and mutually independent and can be connected by transformations via the real-space grid. This multi-basis feature renders GPAW highly versatile and unique among similar codes. By virtue of its modular structure, the GPAW code constitutes an ideal platform for the implementation of new features and methodologies. Moreover, it is well integrated with the Atomic Simulation Environment (ASE), providing a flexible and dynamic user interface. In addition to ground-state DFT calculations, GPAW supports many-body GW band structures, optical excitations from the Bethe–Salpeter Equation, variational calculations of excited states in molecules and solids via direct optimization, and real-time propagation of the Kohn–Sham equations within time-dependent DFT. A range of more advanced methods to describe magnetic excitations and non-collinear magnetism in solids are also now available. In addition, GPAW can calculate non-linear optical tensors of solids, charged crystal point defects, and much more. Recently, support for graphics processing unit (GPU) acceleration has been achieved with minor modifications to the GPAW code thanks to the CuPy library. We end the review with an outlook, describing some future plans for GPAW.
Modeling chemical reactions with quantum chemical methods is challenging when the electronic structure varies significantly throughout the reaction and when electronic excited states are involved. Multireference methods, such as complete active space self-consistent field (CASSCF), can handle these multiconfigurational situations. However, even if the size of the needed active space is affordable, in many cases, the active space does not change consistently from reactant to product, causing discontinuities in the potential energy surface. The localized active space SCF (LASSCF) is a cheaper alternative to CASSCF for strongly correlated systems with weakly correlated fragments. The method is used for the first time to study a chemical reaction, namely the bond dissociation of a mono-, di-, and triphenylsulfonium cation. LASSCF calculations generate smooth potential energy scans more easily than the corresponding, more computationally expensive CASSCF calculations while predicting similar bond dissociation energies. Furthermore, our calculations suggest a homolytic bond cleavage for di- and triphenylsulfonium and a heterolytic pathway for monophenylsulfonium.
Photochemical reactions often involve states that are closely coupled due to near degeneracies, for example by proximity to conical intersections. Therefore, a multistate method is used to accurately describe these states; for example, ordinary perturbation theory is replaced by quasidegenerate perturbation theory. Multiconfiguration pair-density functional theory (MC-PDFT) provides an efficient way to approximate the full dynamical correlation energy of strongly correlated systems, and we recently proposed compressed multistate pair-density functional theory (CMS-PDFT) to treat closely coupled states. In the present paper, we report the implementation of analytic gradients for CMS-PDFT in both OpenMolcas and PySCF, and here we illustrate the use of these gradients by applying the method to the excited states of formaldehyde and phenol.
Electrons lenses produce a high-intensity electron beam and have a variety of applications to circular hadron accelerators. Electron beams of different transverse cross sections and distributions may be designed, depending on the desired application, and they are produced and steered along the orbit of the hadron beam, overlapping with it for typical distances of a few meters before being deflected away and disposed of. Hollow electron beams find applications to high-intensity beam collimation for machines like the CERN Large Hadron Collider (LHC). Such devices can be integrated in a collimation system to improve the halo-cleaning performance through an active control of the halo dynamics: the annular distribution of the electrons excites resonantly the beam tails surrounding the beam core, while the core itself remains unperturbed, as ideally it only “sees” the field-free “hole” in the electron distribution. Hollow electron lenses are part of the upgrade baseline of the High-Luminosity project of the LHC (HL-LHC) and will be installed in the machine during a long shutdown in 2025–2027 to mitigate effects from beam losses so to improve the collimation system performance. This paper describes the hollow electron lens project within the HL-LHC collimation upgrade.
We present the discovery of only the third brown dwarf known to eclipse a non-accreting white dwarf. Gaia parallax information and multicolour photometry confirm that the white dwarf is cool (9950 ± 150 K) and has a low mass (0.45 ± 0.05 M ⊙ ), and spectra and light curves suggest the brown dwarf has a mass of 0.067 ± 0.006 M ⊙ (70M Jup ) and a spectral type of L5 ± 1. The kinematics of the system show that the binary is likely to be a member of the thick disc and therefore at least 5-Gyr old. In conclusion, the high-cadence light curves show that the brown dwarf is inflated, making it the first brown dwarf in an eclipsing white dwarf-brown dwarf binary to be so.
ABSTRACT A promising progenitor scenario for Type Ia supernovae (SNeIa) is the thermonuclear detonation of a white dwarf in a close binary system with another white dwarf. After the primary star explodes, the surviving donor can be spontaneously released as a hypervelocity runaway. One such runaway donor candidate is LP 398-9, whose orbital trajectory traces back ≈105 yr to a known supernova remnant. Here, we report the discovery of carbon-rich circumstellar material around LP 398-9, revealed by a strong infrared excess and analysed with follow-up spectroscopy. The circumstellar material is most plausibly composed of inflated layers from the star itself, mechanically and radioactively heated by the past companion’s supernova. We also detect a 15.4 h periodic signal in the UV and optical light curves of LP 398-9, which we interpret as surface rotation. The rotation rate is consistent with theoretical predictions from this supernova mechanism, and the brightness variations could originate from surface inhomogeneity deposited by the supernova itself. Our observations strengthen the case for this double-degenerate SNIa progenitor channel, and motivate the search for more runaway SNIa donors.
The odd-Z 251 Md nucleus was studied using combined γ-ray and conversion-electron in-beam spectroscopy. Besides the previously observed rotational band based on the [521]1/2 - configuration, another rotational structure has been identified using γ-γ coincidences. The use of electron spectroscopy allowed the rotational bands to be observed over a larger rotational frequency range. Using the transition intensities that depend on the gyromagnetic factor, a [514]7/2 - single-particle configuration has been inferred for this band, i.e., the ground-state band. A physical background that dominates the electron spectrum with an intensity of ≃60% was well reproduced by simulating a set of unresolved excited bands. Moreover, a detailed analysis of the intensity profile as a function of the angular momentum provided a method for deriving the orbital gyromagnetic factor, namely g K = $0.69$ $^{+0.19}_{-0.16}$ for the ground-state band. The odd-Z 249 Md was studied using γ-ray in-beam spectroscopy. Evidence for octupole correlations resulting from the mixing of the Δl = Δ j = 3 [521]3/2 - and [633]7/2 + Nilsson orbitals were found in both 249,251 Md. Here, a surprising similarity of the 251 Md ground-state band transition energies with those of the excited band of 255 Lr has been discussed in terms of identical bands. Lastly, Skyrme-Hartree-Fock-Bogoliubov calculations were performed to investigate the origin of the similarities between these bands.
Cosmic-ray antideuterons could be a key for the discovery of exotic phenomena in our Galaxy, such as dark-matter annihilations or primordial black hole evaporation. Unfortunately the theoretical predictions of the antideuteron flux at Earth are plagued with uncertainties from the mechanism of antideuteron production and propagation in the Galaxy. We present the most up-to-date calculation of the antideuteron fluxes from cosmic-ray collisions with the interstellar medium and from exotic processes. We include for the first time the antideuteron inelastic interaction cross section recently measured by the ALICE collaboration to account for the loss of antideuterons during propagation. In order to bracket the uncertainty in the expected fluxes, we consider several state-of-the-art models of antideuteron production and of cosmic-ray propagation.
Not Available
An efficient and accurate approach for calculating exact exchange and other two-electron integrals has been developed for periodic electronic structure methods. Traditional approaches used for integrating over the Brillouin zone in band structure calculations, e.g. trapezoidal or Monkhorst-Pack, are not accurate enough for two-electron integrals. This is because their integrands contain multiple singularities over the double integration of the Brillouin zone, which with simple integration methods lead to very inaccurate results. A common approach to this problem has been to replace the Coulomb interaction with a screened Coulomb interaction that removes singularities from the integrands in the two-electron integrals, albeit at the inelegance of having to introduce a screening factor which must precomputed or guessed. Instead of introducing screened Coulomb interactions in an ad hoc way, the method developed in this work derives an effective screened potential using a Filon-like integration approach that is based only on the lattice parameters. This approach overcomes the limitations of traditionally defined screened Coulomb interactions for calculating two-electron integrals, and makes chemistry many-body calculations tractable in periodic boundary conditions. This method has been applied to several systems for which conventional DFT methods do not work well, including the reaction pathways for the addition of H 2 to phenol and Au$^{–}_{20}$ nanoparticle, and the electron transfer of a charge trapped state in the Fe(II) containing mica, annite.
Each of the two proton beams in the High-Luminosity Large Hadron Collider (HL-LHC) will carry a total energy of 720 MJ. One concern for machine protection is the energy stored in the transverse beam tails, estimated to potentially reach up to 5% of the total stored energy. Several failure scenarios could drive these tails into the collimators, potentially causing damage and therefore severely affecting operational efficiency. Hollow Electron Lenses (HEL) were integrated in the HL-LHC baseline to mitigate this risk by depleting the tails in a controlled way. A hollow-shaped electron beam runs co-axially to the hadron beam over about 3 m, such that halo particles at large amplitudes become unstable, while core particles ideally remain undisturbed. Residual fields from e-beam asymmetries can, however, induce emittance growth of the beam core. Various options for the pulsing of the HEL are considered and are compared using two figures of merit: halo depletion efficiency and core emittance growth. This contribution presents simulations for these two effects with different HEL pulsing modes using the final HL-LHC optics, that was optimized at the location of the lenses.
Sub-GeV thermal relic dark matter typically requires the existence of a light mediator particle. We introduce the light two-Higgs-doublet portal, illustrated by a minimal UV-complete model for sub-GeV dark matter with kinematically forbidden annihilations into leptons. All new physics states in this scenario lie at or below the electroweak scale, affecting Higgs physics, the muon anomalous magnetic moment and potentially neutrino masses. Observation of radiative dark matter annihilation by future MeV gamma-ray telescopes would be key to unambiguously identify the scenario.