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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Atomic data for ZN II: improving spectral diagnostics of chemical evolution in high-redshift galaxies

Damped Lyα (DLA) and sub-DLA absorbers in quasar spectra provide the most sensitive tools for measuring the element abundances of distant galaxies. The estimation of abundances from absorption lines depends sensitively on the accuracy of the atomic data used. We have started a project to produce new atomic spectroscopic parameters for optical and UV spectral lines using state-of-the-art computer codes employing a very broad configuration interaction (CI) basis. Here we report our results for Zn ii, an ion used widely in studies of the interstellar medium (ISM) as well as DLAs and sub-DLAs. We report new calculations of many energy levels of Zn ii and the line strengths of the resulting radiative transitions. Our calculations use the CI approach within a numerical Hartree–Fock framework. We use both nonrelativistic and quasi-relativistic one-electron radial orbitals. We have incorporated the results of these atomic calculations into the plasma simulation code Cloudy and applied them to a lab plasma and examples of a DLA and a sub-DLA. Our values of the Zn ii λλ 2026, 2062 oscillator strengths are higher than previous values by 0.10 dex. The Cloudy calculations for representative absorbers with the revised Zn atomic data imply ionization corrections lower than calculated earlier by 0.05 dex. The new results imply that Zn metallicities should be lower by 0.1 dex for DLAs and by 0.13–0.15 dex for sub-DLAs than in past studies. Our results can be applied to other studies of Zn ii in the Galactic and extragalactic ISM.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

Potential energy surfaces of the electronic states of Li{sub 2}F and Li{sub 2}F{sup −}

The potential energy surfaces of the ground and low-lying excited states for the insertion reaction of atomic fluorine (F) and fluoride (F{sup −}) into the dilithium (Li{sub 2}) molecule have been investigated. We have carried out explicitly correlated multi-reference configuration interaction (MRCI-F12) calculations using Dunning’s augmented correlation-consistent basis sets. For the neutral system, the insertion of F into Li{sub 2} proceeds via a harpoon-type mechanism on the ground state surface, involving a covalent state and an ionic state which avoid each other at long distance. A detailed analysis of the changes in the dipole moment along the reaction coordinate reveals multiple avoided crossings among the excited states and shows that the charge-transfer processes play a pivotal role for the stabilization of the low-lying electronic states of Li{sub 2}F. For the anionic system, which is studied for the first time, the insertion of F{sup −} is barrierless for many states and there is a gradual charge transfer from F{sup −} to Li{sub 2} along the reaction path. We also report the optimized parameters and the spectroscopic properties of the five lowest states of the neutral and seven lowest states of the anionic systems, which are strongly stabilized with respect to their respective Li{sub 2} + F/F{sup −} asymptotes. The observed barrierless insertion mechanisms for both systems make them good candidates for investigation under the ultracold regime.

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

Small tensor product distributed active space (STP-DAS) framework for relativistic and non-relativistic multiconfiguration calculations: Scaling from 10 9 on a laptop to 10 12 determinants on a supercomputer

Despite the power and flexibility of configuration interaction (CI) based methods in computational chemistry, their broader application is limited by an exponential increase in both computational and storage requirements, particularly due to the substantial memory needed for excitation lists that are crucial for scalable parallel computing. Here, the objective of this work is to develop a new CI framework, namely, the small tensor product distributed active space (STP-DAS) framework, aimed at drastically reducing memory demands for extensive CI calculations on individual workstations or laptops, while simultaneously enhancing scalability for extensive parallel computing. Moreover, the STP-DAS framework can support various CI-based techniques, such as complete active space (CAS), restricted active space, generalized active space, multireference CI, and multireference perturbation theory, applicable to both relativistic (two- and four-component) and non-relativistic theories, thus extending the utility of CI methods in computational research. We conducted benchmark studies on a supercomputer to evaluate the storage needs, parallel scalability, and communication downtime using a realistic exact-two-component CASCI (X2C-CASCI) approach, covering a range of determinants from 10 9 to 10 12 . Additionally, we performed large X2C-CASCI calculations on a single laptop and examined how the STP-DAS partitioning affects performance.

Complete-active space self-consistent field↗
DOE OSTI2021

Quantum Solvers for Plane-Wave Hamiltonians: Abridging Virtual Spaces Through the Optimization of Pairwise Correlations

For many-body methods such as MCSCF and CASSCF, in which the number of one-electron orbitals is optimized and independent of the basis set used, there are no problems with using plane-wave basis sets. However, for methods currently used in quantum computing such as select configuration interaction (CI) and coupled cluster (CC) methods, it is necessary to have a virtual space that is able to capture a significant amount of electron-electron correlation in the system. The virtual orbitals in a pseudopotential plane-wave Hartree–Fock calculation, because of Coulomb repulsion, are often scattering states that interact very weakly with the filled orbitals. As a result, very little correlation energy is captured from them. The use of virtual spaces derived from the one-electron operators has also been tried, and while some correlations are captured, the amount is quite low. To overcome these limitations, we have been developing new classes of algorithms to define virtual spaces by optimizing orbitals from small pairwise CI Hamiltonians, which we term as correlation optimized virtual orbitals with the abbreviation COVOs. With these procedures, we have been able to derive virtual spaces, containing only a few orbitals, which are able to capture a significant amount of correlation. The focus in this manuscript is on using these derived basis sets to target full CI (FCI) quality results for H2 on near-term quantum computers. However, the initial results for this approach were promising. We were able to obtain good agreement with FCI/cc-pVTZ results for this system with just 4 virtual orbitals, using both FCI and quantum simulations. The quality of the results using COVOs suggests that it may be possible to use them in other many-body approaches, including coupled cluster and Møller–Plesset perturbation theories, and open up the door to many-body calculations for pseudopotential plane-wave basis set methods.

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

Global triplet potential energy surfaces for the N{sub 2}(X{sup 1}Σ) + O({sup 3}P) → NO(X{sup 2}Π) + N({sup 4}S) reaction

This work presents two global triplet potential energy surfaces (PESs) for the high-energy reaction N{sub 2}(X{sup 1}Σ) + O({sup 3}P) → NO(X{sup 2}Π) + N({sup 4}S)—in particular, for the lowest energy {sup 3}A′ and {sup 3}A″ PESs. In order to obtain the energies needed for fitting analytic surfaces, we carried out multireference configuration interaction (MRCI) calculations based on wave functions obtained from state-averaged complete active space self-consistent field calculations for 2280 geometries for the three lowest {sup 3}A″ states and for 2298 geometries for the three lowest {sup 3}A′ states. The lowest-energy {sup 3}A′ and {sup 3}A″ states at each of these geometries were then improved by applying the dynamically scaled external correlation (DSEC) method to all MRCI points, and the resulting DSEC energies were used for construction of the ground-state PES for each symmetry. The many-body component of the DSEC energies for the three-dimensional {sup 3}A′ and {sup 3}A″ PESs was then least-squares fitted in terms of permutationally invariant polynomials in mixed exponential–Gaussian bond order variables. The global and local minima as well as the transition structures of both the {sup 3}A′ and the {sup 3}A″ analytic PES were explored. In agreement with previous work, we find that the reverse reaction is barrierless on the {sup 3}A″ surface along the minimum energy pathway. However, we have explored several new local minima and transition structures on the {sup 3}A′ PES. Furthermore, based on the newly found minima and transition structures, two independent reaction mechanisms have been illustrated for the reaction path on the {sup 3}A′ PES. The analytic surfaces may be used for dynamics calculations of electronically adiabatic reactive scattering and energy transfer.

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

P SI4 1.4: Open-source software for high-throughput quantum chemistry

PSI4 is a free and open-source ab initio electronic structure program providing implementations of Hartree–Fock, density functional theory, many-body perturbation theory, configuration interaction, density cumulant theory, symmetry-adapted perturbation theory, and coupled-cluster theory. Most of the methods are quite efficient, thanks to density fitting and multi-core parallelism. The program is a hybrid of C++ and Python, and calculations may be run with very simple text files or using the Python API, facilitating post-processing and complex workflows; method developers also have access to most of PSI4 's core functionalities via Python. Job specification may be passed using The Molecular Sciences Software Institute (MolSSI) QCSCHEMA data format, facilitating interoperability. We announce a rewrite of our top-level computation driver, and concomitant adoption of the MolSSI QCARCHIVE INFRASTRUCTURE project, makes the latest version of PSI4 well suited to distributed computation of large numbers of independent tasks. The project has fostered the development of independent software components that may be reused in other quantum chemistry programs.

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

Theoretical calculations of rotationally inelastic collisions of He with NaK(A {sup 1}Σ{sup +}): Transfer of population, orientation, and alignment

We have performed extensive calculations to investigate thermal energy, rotationally inelastic collisions of NaK (A{sup 1}Σ{sup +}) with He. We determined a potential energy surface using a multi-reference configuration interaction wave function as implemented by the GAMESS electronic structure code, and we have performed coupled channel scattering calculations using the Arthurs and Dalgarno formalism. We also calculate the Grawert coefficients B{sub λ}(j, j′) for each j → j′ transition. These coefficients are used to determine the probability that orientation and alignment are preserved in collisions taking place in a cell environment. The calculations include all rotational levels with j or j′ between 0 and 50, and total (translational and rotational) energies in the range 0.0002–0.0025 a.u. (∼44–550 cm{sup −1}). The calculated cross sections for transitions with even values of Δj tend to be larger than those for transitions with odd Δj, in agreement with the recent experiments of Wolfe et al. (J. Chem. Phys. 134, 174301 (2011)). The calculations of the energy dependence of the cross sections and the calculations of the fraction of orientation and alignment preserved in collisions also exhibit distinctly different behaviors for odd and even values of Δj. The calculations also indicate that the average fraction of orientation or alignment preserved in a transition becomes larger as j increases. We interpret this behavior using the semiclassical model of Derouard, which also leads to a simple way of visualizing the distribution of the angles between the initial and final angular momentum vectors j and j′. Finally, we compare the exact quantum results for j → j′ transitions with results based on the simpler, energy sudden approximation. That approximation is shown to be quite accurate.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 package

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design.

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

Electron correlation within the relativistic no-pair approximation

This paper addresses the definition of correlation energy within 4-component relativistic atomic and molecular calculations. In the nonrelativistic domain the correlation energy is defined as the difference between the exact eigenvalue of the electronic Hamiltonian and the Hartree-Fock energy. In practice, what is reported is the basis set correlation energy, where the “exact” value is provided by a full Configuration Interaction (CI) calculation with some specified one-particle basis. The extension of this definition to the relativistic domain is not straightforward since the corresponding electronic Hamiltonian, the Dirac-Coulomb Hamiltonian, has no bound solutions. Present-day relativistic calculations are carried out within the no-pair approximation, where the Dirac-Coulomb Hamiltonian is embedded by projectors eliminating the troublesome negative-energy solutions. Hartree-Fock calculations are carried out with the implicit use of such projectors and only positive-energy orbitals are retained at the correlated level, meaning that the Hartree-Fock projectors are frozen at the correlated level. We argue that the projection operators should be optimized also at the correlated level and that this is possible by full Multiconfigurational Self-Consistent Field (MCSCF) calculations, that is, MCSCF calculations using a no-pair full CI expansion, but including orbital relaxation from the negative-energy orbitals. We show by variational perturbation theory that the MCSCF correlation energy is a pure MP2-like correlation expression, whereas the corresponding CI correlation energy contains an additional relaxation term. We explore numerically our theoretical analysis by carrying out variational and perturbative calculations on the two-electron rare gas atoms with specially tailored basis sets. In particular, we show that the correlation energy obtained by the suggested MCSCF procedure is smaller than the no-pair full CI correlation energy, in accordance with the underlying minmax principle and our theoretical analysis. We also show that the relativistic correlation energy, obtained from no-pair full MCSCF calculations, scales at worst as X{sup −2} with respect to the cardinal number X of our correlation-consistent basis sets optimized for the two-electron atoms. This is better than the X{sup −1} scaling suggested by previous studies, but worse than the X{sup −3} scaling observed in the nonrelativistic domain. The well-known 1/Z- expansion in nonrelativistic atomic theory follows from coordinate scaling. We point out that coordinate scaling for consistency should be accompanied by velocity scaling. In the nonrelativistic domain this comes about automatically, whereas in the relativistic domain an explicit scaling of the speed of light is required. This in turn explains why the relativistic correlation energy to the lowest order is not independent of nuclear charge, in contrast to nonrelativistic theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Theoretical study of the 7Sigma(u)+ state of N2

Theoretical potentials for the 7Sigma(u)+ state are reported using both extended Slater and Gaussian basis sets. Electron correlation is included using the interacting correlated fragments (ICF), the singles plus doubles configuration-interaction (SDCI), and the coupled-pair functional (CPF) approaches. The best potential, corrected for basis set superposition errors, has a well depth of about 21/cm and an r(e) of 7.52 bohr. The inclusion of the nitrogen 2s correlation significantly increases the well depth. These results are in reasonably good agreement with the empirical potential of Ferrante and Stwalley (1983), and support the contention that spin-polarized atomic nitrogen should behave like a classical solid such as Ne. It is shown that the modified Buckingham potential used by Ferrante and Stwalley is consistent with the present ab initio potentials if smaller values are used for the dispersion coefficients of the nitrogen atom.

Partridge, H.↗
NASA NTRS1976

A wing-jet interaction theory for USB configurations

The aerodynamic interaction between the wing and an inviscid upper-surface blowing (USB) thick jet with Mach number nonuniformity is treated within the framework of a linear inviscid subsonic compressible flow theory. A two-vortex-sheet model for the jet surface is used to represent the induced flowfields inside and outside the jet. Comparison of the predicted results with experimental data shows good agreement in lift, induced drag, and pitching moment. It is shown that the thin jet flap theory is inadequate for USB configurations with thick jet.

Lan, C. E.↗
NASA NTRS1980

Quasi-projection-operator calculation of inelastic resonances in He/-/ and Li

Feshbach resonances of electrons incident of He and Li(+) are calculated below the 3(S-3) target threshold by means of the inelastic quasi-projection-operator technique of Temkin and Bhatia (1972). A configuration-interaction-type wave function is employed with up to 46 configurations. The calculations reveal, with reasonable accuracy, all presently observed Feshbach resonances. The method does not reveal shape resonances, but, for isoelectronic systems with greater nuclear charge, it is argued that shape resonance should become less important. This is already apparent in the case of Li, for which the known resonances are calculated and higher resonances, for which there are as yet no experimental data, are predicted.

Wakid, S.↗
DOE OSTI2020

Accurate prediction of core-level spectra of radicals at density functional theory cost via square gradient minimization and recoupling of mixed configurations

State-specific orbital optimized approaches are more accurate at predicting core-level spectra than traditional linear-response protocols, but their utility had been restricted due to the risk of "variational collapse" down to the ground state. We employ the recently developed square gradient minimization algorithm to reliably avoid variational collapse and study the effectiveness of orbital optimized density functional theory (DFT) at predicting second period element 1s core-level spectra of open-shell systems. Several density functionals (including SCAN, B3LYP, and ωB97X-D3) are found to predict excitation energies from the core to singly occupied levels with high accuracy (≤0.3 eV RMS error) against available experimental data. Higher excited states are, however, more challenging by virtue of being intrinsically multiconfigurational. We thus present a configuration interaction inspired route to self-consistently recouple single determinant mixed configurations obtained from DFT, in order to obtain approximate doublet states. This recoupling scheme is used to predict the C K-edge spectra of the allyl radical, the O K-edge spectra of CO + , and the N K-edge of NO 2 with high accuracy relative to experiment, indicating substantial promise in using this approach for the computation of core-level spectra for doublet species [vs more traditional time dependent DFT, equation of motion coupled cluster singles and doubles (EOM-CCSD), or using unrecoupled mixed configurations]. Finally, we also present general guidelines for computing core-excited states from orbital optimized DFT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

A simple interpretation of the Fe2(-) photoelectron spectrum

The photoelectron spectrum of Fe2(-) can be simply interpreted in terms of electron detachment from the mildly bonding 4s sigma sup * sub u orbital of a (4s sigma sub s)(sup 2) (4s sigma sup * sub u)(sup 2) (3d)(sup 13) anion. This interpretation implies a (4s sigma sub g)(sup 2) (4s sigma sup * sub u)(sup1) (3d)(sup13) configuration for the ground state of Fe2, correlating with one ground state (4s2 3d6) and one excited state (4s1 3d7) Fe atom. A comparison of the bond length and vibrational frequency of Fe2 to values for transition metal dimers containing single 4s-4s bonds is suggestive of 3d-3d bonding in this molecule. The results of preliminary full-valence configuration interaction calculations provide stron support for the proposed Fe2 and Fe2(-) configurations.

Leopold, Doreen G.↗
DOE OSTI2019

Spatial solitary like weak probe wave in the three-level Λ-type atoms

We study the interaction of the medium composed of three-level atoms in A configuration interacting with two laser fields: weak probe field and strong control field. The probe field enters the medium under a certain angle, and it is initially in the form of the spatial soliton, while the control field is periodically modulated. The system of optical Bloch equations is analytically solved in the stationary regime by the perturbation method in order to obtain linear and third-order nonlinear susceptibility of the medium with respect to the probe field. After a straightforward algebraic procedure, using the approximation of the slow-varying field envelope, the nonlinear Schrödinger equation for the probe field is obtained. It is numerically solved by applying the spectral Fourier split-step method. It is found that, for properly chosen values of the probe and control field detunings and control Rabi frequency, the probe field behaves as a solitary wave whose direction does not depend on the incident angle. Moreover, the regime consisting of Bloch-like oscillations can be identified. The simulation is performed by choosing the corresponding levels of Mg atoms. © 2019 Author(s).

60 APPLIED LIFE SCIENCES↗
NASA NTRS1971

One-center r sub ij integrals over Slater-type orbitals.

Expressions are derived for the integrals which arise in calculations of atomic wavefunctions of four or more electrons, using the method of explicit introduction of interelectronic distances into a configuration interaction wavefunction (subject to the restriction of at most one interelectronic distance per configuration). The approach followed in the derivations is similar to one followed by OEhrn and Nordling for three electron integrals; however, in extending the OEhrn and Nordling scheme to four electrons for a basis of s, p, and d Slater-type orbitals, numerical snags are encountered which have been obviated by a Euler transformation on certain of the auxiliary integrals.

Sims, J. S.↗
NASA NTRS1989

Atomic data for opacity calculations. X - Oscillator strengths and photoionisation cross sections for O III

Energy levels and electric dipole radiative transitions were determined for O III. The wavefunctions for the bound and continuum states were derived by solving coupled integrodifferential equations in the close-coupling approximation with the aid of two methods, the R-matrix and linear algebraic methods. Configuration interaction wavefunctions are presented for eight states of the O IV target with configurations of 2s(x)sp(y) (x + y = 3). Oscillator strengths are calculated for the transitions between, and photoionization cross sections from, bound states of O III with configurations of 2s(x)2p(y)nl (for n of not greater than 10 and l of not greater than 3).

Luo, D.↗
NASA NTRS1973

Excited electronic states of O2/-/.

Configuration interaction (CI) variational trial functions (which assure formally correct dissociation) and the single-configuration self-consistent-field approximation are applied to the calculation of the excited electronic states of the negatively charged oxygen molecule. The energy curves and wave functions of these states are analyzed. All the excited states are found to have equilibrium-internuclear separations at least 1 a.u. larger than the ground state. The two lowest energy states are characterized, respectively, as shape and valence Feshbach resonances.

Krauss, M.↗