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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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14 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Orbital optimisation in the perfect pairing hierarchy: applications to full-valence calculations on linear polyacenes

Here, we describe the implementation of orbital optimisation for the models in the perfect pairing hierarchy. Orbital optimisation, which is generally necessary to obtain reliable results, is pursued at perfect pairing (PP) and perfect quadruples (PQ) levels of theory for applications on linear polyacenes, which are believed to exhibit strong correlation in the π space. While local minima and σ-π symmetry breaking solutions were found for PP orbitals, no such problems were encountered for PQ orbitals. The PQ orbitals are used for single-point calculations at PP, PQ and perfect hextuples (PH) levels of theory, both only in the π subspace, as well as in the full σπ valence space. It is numerically demonstrated that the inclusion of single excitations is necessary also when optimised orbitals are used. PH is found to yield good agreement with previously published density matrix renormalisation group data in the π space, capturing over 95% of the correlation energy. Full-valence calculations made possible by our novel, efficient code reveal that strong correlations are weaker when larger basis sets or active spaces are employed than in previous calculations. The largest full-valence PH calculations presented correspond to a (192e,192o) problem.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Wavefunction stability analysis without analytical electronic Hessians: application to orbital-optimised second-order Møller–Plesset theory and VV10-containing density functionals

Wavefunction stability analysis is commonly applied to converged self-consistent field (SCF) solutions to verify whether the electronic energy is a local minimum with respect to second-order variations in the orbitals. By iterative diagonalisation, the procedure calculates the lowest eigenvalue of the stability matrix or electronic Hessian. However, analytical expressions for the electronic Hessian are unavailable for most advanced post-Hartree-Fock (HF) wave function methods and even some Kohn-Sham (KS) density functionals. To address such cases, here we formulate the Hessian-vector product within the iterative diagonalisation procedure as a finite difference of the electronic gradient with respect to orbital perturbations in the direction of the vector. As a model application, following the lowest eigenvalue of the orbital-optimised second-order Møller-Plesset perturbation theory (OOMP2) Hessian during H 2 dissociation reveals the surprising stability of the spin-restricted solution at all separations, with a second independent unrestricted solution. We show that a single stable solution can be recovered by using the regularised OOMP2 method (δ-OOMP2), which contains a level shift. Internal and external stability analyses are also performed for SCF solutions of a recently developed range-separated hybrid density functional, ωB97X-V, for which the analytical Hessian is not yet available due to the complexity of its long-range non-local VV10 correlation functional.

Brueckner orbitals↗
DOE OSTI2019

The all configuration mean energy multiconfiguration self-consistent-field method. I. Equal configuration weights

The All Configuration Mean Energy (ACME) conditions are a special case of state averaging for Multiconfigurational Self-Consistent-Field (MCSCF) orbital optimisation. The method is formulated using the Graphical Unitary Group Approach (GUGA) in which the Configuration State Function (CSF) basis is represented as walks within a Shavitt graph. This graphical formulation leads to efficient recursive algorithms for the energy and reduced density matrices (RDM) that are independent of the CSF dimension and that scale only as O(n2) where n is the number of occupied orbitals. The Hamiltonian matrix diagonalization step is obviated and the CSF expansion coefficients are neither referenced nor required. This allows MCSCF orbital optimisation to be performed for essentially unlimited numbers of active orbitals and arbitrarily large CSF expansions. The discussion includes various types of CSF expansion spaces, the partitioning of the essential and redundant orbital optimisation parameters, the computation of the spin-density, and the formulation of state-specific analytic gradients and nonadiabatic coupling for high-level electronic structure methods that use the ACME MCSCF orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Linear-scaling time-dependent density-functional theory beyond the Tamm-Dancoff approximation: Obtaining efficiency and accuracy with in situ optimised local orbitals

We present a solution of the full time-dependent density-functional theory (TDDFT) eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspaces with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate gradient algorithm that is very memory-efficient. The algorithm is validated on a small test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of bacteriochlorophyll in solution. The largest systems considered in this work are of the same order of magnitude as a variety of widely studied pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Explicitly correlated coupled-cluster theory with Brueckner orbitals

Brueckner orbitals are the optimal orbitals for use in F12 explicitly correlated coupled-cluster (CC) treatments. A novel approach, Brueckner coupled-cluster doubles with perturbative triples BCCD(T){sub (F12*)} is presented that avoids the expensive re-evaluation of F12 integrals throughout the orbital optimisation and includes a newly derived basis set correction to the Brueckner reference energy. The generalisation of F12 theory to arbitrary non-Hartree–Fock references and to Fock operators that include scalar relativistic effects is also presented. The performance of the new Brueckner F12 method is assessed for a test set of 50 open- and closed-shell reactions and for the ionisation potentials and electron affinities (EAs) of the first-row transition metal atoms. Benchmark basis set limit coupled-cluster singles, doubles and perturbative triples (CCSD(T)) and BCCD(T) values are reported for all energies in the test sets. BCCD(T){sub (F12*)} performs systematically better than CCSD(T)(F12*) for electron affinities where orbital relaxation effects are significant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A correction for the Hartree-Fock density of states for jellium without screening

We revisit the Hartree-Fock (HF) calculation for the uniform electron gas, or jellium model, whose predictions—divergent derivative of the energy dispersion relation and vanishing density of states (DOS) at the Fermi level—are in qualitative disagreement with experimental evidence for simple metals. Currently, this qualitative failure is attributed to the lack of screening in the HF equations. Employing Slater’s hyper-Hartree-Fock (HHF) equations, derived variationally, to study the ground state and the excited states of jellium, we find that the divergent derivative of the energy dispersion relation and the zero in the DOS are still present, but shifted from the Fermi wavevector and energy of jellium to the boundary between the set of variationally optimised and unoptimised HHF orbitals. The location of this boundary is not fixed, but it can be chosen to lie at arbitrarily high values of wavevector and energy, well clear from the Fermi level of jellium. We conclude that, rather than the lack of screening in the HF equations, the well-known qualitative failure of the ground-state HF approximation is an artifact of its nonlocal exchange operator. Other similar artifacts of the HF nonlocal exchange operator, not associated with the lack of electronic correlation, are known in the literature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

A linear surrogate for optimising functions of an orthogonal matrix with applications in wave function theory

The technique of surrogate optimisation is to use a simpler function to approximate a complex function that is time-consuming to evaluate. Here we show that the maximum of a special type of surrogate function f(U)=Tr(AU),UϵO(n) is at A T (AA T ) 1/2 , and that there is one and only one local maximum both in SO(n) and O(n)–SO(n). This function f(U) has been found to be useful in various aspects of electronic structure theory, including proving the Carlson-Keller theorem, and localising orbitals. As one other example, we apply it here to optimise the ground state of molecules using the Generalised Valence Bond wavefunction.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Understanding the Electronic and Structural Effects in ORR Intermediate Binding on Anion‐Substituted Zirconia Surfaces

Abstract For oxygen reduction reaction (ORR), the surface adsorption energies of O and OH* intermediates are key descriptors for catalytic activity. In this work, we investigate anion‐substituted zirconia catalyst surfaces and determine that adsorption energies of O and OH* intermediates is governed by both structural and electronic effects. When the adsorption energies are not influenced by the structural effects of the catalyst surface, they exhibit a linear correlation with integrated crystal orbital Hamiltonian population (ICOHP) of the adsorbate‐surface bond. The influence of structural effects, due to the re‐optimisation slab geometry after adsorption of intermediate species, leads to stronger adsorption of intermediates. Our calculations show that there is a change in the bond order to accommodate the incoming adsorbate species which leads to stronger adsorption when both structural and electronic effects influence the adsorption phenomena. The insights into the catalyst‐adsorbate interactions can guide the design of future ORR catalysts.

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

Comparative collisionless alpha particle confinement in stellarator reactors with the XGC gyrokinetic code

Whole volume simulations of stellarators are necessary to address a number of important physics and engineering issues, including turbulent transport prediction and optimising divertor operation. In this work, advances in development of a whole volume stellarator capability for the global gyrokinetic particle-in-cell code XGC are detailed. A 3D interpolation of the equilibrium magnetic eld to the last close flux surface, calculated using the VMEC ideal magnetohydrodynamic equilibrum code, has been implemented. Orbit tracing with the XGC code is verified for the Wendelstein 7-X stellarator by comparison with the BEAMS3D and EUTERPE codes. The XGC stellarator version has then been used to consider collisionless alpha particle con nement in representative quasi-isodynamic and quasi-axisymmetric designs. It has been shown that, at least without further optimisation for energetic particle confinement, the Wendelstein 7-X-like quasi-isodynamic reactor design exhibits better alpha particle confinement.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

A local framework for calculating coupled cluster singles and doubles excitation energies (LoFEx-CCSD)

Here, the recently developed Local Framework for calculating Excitation energies (LoFEx) is extended to the coupled cluster singles and doubles (CCSD) model. In the new scheme, a standard CCSD excitation energy calculation is carried out within a reduced excitation orbital space (XOS), which is composed of localised molecular orbitals and natural transition orbitals determined from time-dependent Hartree–Fock theory. The presented algorithm uses a series of reduced second-order approximate coupled cluster singles and doubles (CC2) calculations to optimise the XOS in a black-box manner. This ensures that the requested CCSD excitation energies have been determined to a predefined accuracy compared to a conventional CCSD calculation. We present numerical LoFEx-CCSD results for a set of medium-sized organic molecules, which illustrate the black-box nature of the approach and the computational savings obtained for transitions that are local compared to the size of the molecule. In fact, for such local transitions, the LoFEx-CCSD scheme can be applied to molecular systems where a conventional CCSD implementation is intractable.

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

Orange Fluorescent Ru(III) Complexes Based on 4′-Aryl Substituted 2,2′:6′,2″-Terpyridine for OLEDs Application

A series of ruthenium (III) complexes of the formulae [Ru(4-Mephtpy){sub 2}]Cl{sub 3}(1) [Ru(L{sub 1})], [Ru(3,4,5-tmphtpy){sub 2}]Cl{sub 3}(2) [Ru(L{sub 2})], and [Ru(4-thptpy){sub 2}]Cl{sub 3}(3) [Ru(L{sub 3})], (where L = terpy = 2.2′:6′2″ terpyridine ligands) are synthesized. The complexes were characterized by elemental analyses, spectroscopic and electrochemical data. The density functional theory (DFT) outlines the geometric optimisation and electronic charge transition of these complexes. Photophysical studies describe that the luminescence of Ru(III) complexes is due to electronic transition between the energy levels of singly unoccupied molecular orbitals (SUMO) and singly occupied molecular orbitals (SOMO). It also exhibits the potential charge transfer to π–π* and n–π* states due to MLCT and ILCT processes of the complexes. The observed bands centered at 591 and 620 nm demonstrate that these emissions originated from the transition of SUMO to SOMO energy levels, that is, from the radiative decay from the doublet exciton. Due to the heavy metal effect of Ru(III) ions the photophysical behaviour depends on the MLCT process. In conclusion, that the all three Ru(L{sub 1}-L{sub 3}) complexes are fallen orange emission.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2016

Interstellar laser communication: implementability criterion and optimisation conditions for the addressed signal search and sending

Using new opportunities offered by the construction of large optical telescopes, a laser radiation receiver with an iodine active quantum filter, high-energy iodine lasers with a diffraction-limited beam divergence and the discovery of exoplanets of the Earth type, including those located relatively not far from the Sun, we analyse the implementability of interstellar laser communication under the conditions, when the central spot of the diffraction pattern at the place of the laser signal reception by means of large optical telescopes can be made smaller than the orbit of the planet, and the signals come to the specified point of the orbit not synchronously with the planet motion because of the error in the determination of the distance between the Sun and the star, around which the planet chosen for communication rotates. (paper)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

Thin-film X-ray filters on microstructured substrates and their thermophysical properties

It is shown that structured substrates having micron- or submicron-sized through holes and coated with an ultrathin organic film can be used for the fabrication of thin-film X-ray filters via direct growth of functional layers on a substrate by sputter deposition, without additional complex processing steps. An optimised process is considered for the fabrication of X-ray filters on support structures in the form of electroplated fine nickel grids and on track-etched polymer membranes with micron- and submicron-diameter through pores. ‘Optimisation’ is here taken to mean matching the sputter deposition conditions with the properties of substrates so as to avoid overheating. The filters in question are intended for both imaging and single-channel detectors operating in the soft X-ray and vacuum UV spectral regions, at wavelengths from 10 to 60 nm. Thermal calculations are presented for the heating of ultrathin layers of organic films and thin-film support substrates during the sputter deposition of aluminium or other functional materials. The paper discusses approaches for cooling thin-film composites during the sputter deposition process and the service of the filters in experiments and gives a brief overview of the works that utilised filters produced by the described technique on microstructured substrates, including orbital solar X-ray research in the framework of the CORONAS programme and laboratory laser plasma experiments. (invited paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

New linear stability parameter to describe low-β electromagnetic microinstabilities driven by passing electrons in axisymmetric toroidal geometry

In magnetic confinement fusion devices, the ratio of the plasma pressure to the magnetic field energy, β, can become sufficiently large that electromagnetic microinstabilities become unstable, driving turbulence that distorts or reconnects the equilibrium magnetic field. In this paper, a theory is proposed for electromagnetic, electron-driven linear instabilities that have current layers localised to mode-rational surfaces and binormal wavelengths comparable to the ion gyroradius. The model retains axisymmetric toroidal geometry with arbitrary shaping, and consists of orbit-averaged equations for the mode-rational surface layer, with a ballooning space kinetic matching condition for passing electrons. The matching condition connects the current layer to the large scale electromagnetic fluctuations, and is derived in the limit that β is comparable to the square root of the electron-to-ion-mass ratio. Electromagnetic fluctuations only enter through the matching condition, allowing for the identification of an effective β that includes the effects of equilibrium flux surface shaping. The scaling predictions made by the asymptotic theory are tested with comparisons to results from linear simulations of micro-tearing and electrostatic microinstabilities in MAST discharge #6252, showing excellent agreement. In particular, it is demonstrated that the effective β can explain the dependence of the local micro-tearing mode (MTM) growth rate on the ballooning parameter θ 0 – possibly providing a route to optimise local flux surfaces for reduced MTM-driven transport.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗