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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

Evaluation of Early Ground Control Station Configurations for Interacting with a UAS Traffic Management (UTM) System

The purpose of this paper is to report on a human factors evaluation of ground control station design concepts for interacting with an unmanned traffic management system. The data collected for this paper comes from recent field tests for NASA's Unmanned Traffic Management (UTM) project, and covers the following topics; workload, situation awareness, as well as flight crew communication, coordination, and procedures. The goal of this evaluation was to determine if the various software implementations for interacting with the UTM system can be described and classified into design concepts to provide guidance for the development of future UTM interfaces. We begin with a brief description of NASA's UTM project, followed by a description of the test range configuration related to a second development phase. We identified (post hoc) two classes in which the ground control stations could be grouped. This grouping was based on level of display integration. The analysis was exploratory and informal. It was conducted to compare ground stations across those two classes and against the aforementioned topics. Herein, we discuss the results.

unmanned traffic management↗
NASA NTRS1992

Photodissociation of CH2. I - Potential energy surfaces of the dissociation into CH and H

The possible photodissociation pathways of the CH2 radical are studied using ab initio multireference configuration-interaction methods, and accurate photodissociation cross sections and branching ratios for the production of CH + H and C + H2 are obtained. Potential energy surfaces were calculated using the Wuppertal-Bonn self-consistent field plus a multireference single and double-excitation configuration interaction package of programs. Two-dimensional potential energy surfaces of the ten lowest triplet states correlating with the seven lowest states of CH were calculated as functions of bond angle and one C-H bond distance, keeping the other C-H bond distance fixed at the equilibrium CH2 value.

Bearda, Robert A.↗
DOE OSTI2020

A benchmark of Gutzwiller conjugate gradient minimization method in ground state energy calculations of dimers

Herein we present numerical results of ground-state energies of 9 molecules in the well-established G2 molecule set given by the Gutzwiller conjugate gradient minimization (GCGM) method. The method, beyond the commonly used Gutzwiller approximation, was recently developed based on Gutzwiller variational wave functions. We find that compared to benchmark data given by full configuration interaction, GCGM total energies are reasonably well reproduced with the minimum basis set. To include the dynamical correlation beyond the minimal basis calculations, we adopt the local density approximation for the dynamical correlation energy $E_c$. By comparing the results with benchmark data given by experiments and large-basis configuration interaction, the GCGM total energies with $E_c$ are in general better reproduced, but discrepancies are still observed for some dimers.

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

Theoretical study of the dipole moment function of OH(X 2Pi)

A complete theoretical electric dipole moment function mu(r) is computed for OH(X 2Pi) at the full configuration-interaction (FCI) level for DZP + diffuse Gaussian basis set. The energy and dipole moment are also determined with 2d functions on oxygen at seven r values. The following methods are compared to the FCI for both the oxygen 1d and 2d basis sets: single-reference singles-plus-doubles configuration interaction (SDCI), SDCI with Davidson's correction, the coupled pair functional approach (CPF) and a modified form of CPF, CASSCF, and CASSCF-MRSDCI, and the external contracted CI(CCI) method. The dipole moments are evaluated both as an expectation value and by finite-field methods. The results support the superiority of evaluating the dipole moment as an energy derivative rather than as an expectation value.

Langhoff, Stephen R.↗
NASA NTRS1985

Oscillator strengths and collision strengths for neutral sulfur

Configuration-interaction target wave functions are used in the present calculation of collision strengths, for electron impact excitation of neutral sulfur from the group 3p4 3P state to excited states 3p3 4s 3S0, 3p3(4S0)3d 3D0, and 3p3 4s 3P0, in a close coupling approximation for the energy range up to 1,000,000 K. Configuration-interaction target wave functions are used in the calculation of collision strengths, and oscillator strengths for various triplet transitions are reported together with transitions between 3p4 1D and 3p4 1S and other singlet-excited states.

Ho, Y. K.↗
DOE OSTI2021

Simulation of adiabatic quantum computing for molecular ground states

Quantum computation promises to provide substantial speedups in many practical applications with a particularly exciting one being the simulation of quantum many-body systems. Adiabatic state preparation (ASP) is one way that quantum computers could recreate and simulate the ground state of a physical system. In this paper, we explore a novel approach for classically simulating the time dynamics of ASP with high accuracy and with only modest computational resources via an adaptive sampling configuration interaction scheme for truncating the Hilbert space to only the most important determinants. We verify that this truncation introduces negligible error and use this new approach to simulate ASP for sets of small molecular systems and Hubbard models. Furthermore, we examine two approaches to speeding up ASP when performed on quantum hardware: (i) using the complete active space configuration interaction (CASCI) wave function instead of the Hartree–Fock initial state and (ii) a nonlinear interpolation between the initial and target Hamiltonians. We find that starting with a CASCI wave function with a limited active space yields substantial speedups for many of the systems examined, while nonlinear interpolation does not. In additional, we observe interesting trends in the minimum gap location (based on the initial state) as well as how state preparation time can depend on certain molecular properties, such as the number of valence electrons. Importantly, we find that the required state preparation times do not show an immediate exponential wall that would preclude an efficient run of ASP on actual hardware.

Kremenetski, Vladimir↗
DOE OSTI2021

Nucleon-pair approximation for nuclei from spherical to deformed regions

Here we model low-lying states of atomic nuclei in the nucleon-pair approximation of the shell model, using three approaches to select collective nucleon pairs: the generalized seniority scheme, the conjugate gradient method, and the Hartree-Fock approach. We find the collective pairs obtained from the generalized seniority scheme provide a good description for nearly spherical nuclei, and those from the conjugate gradient method or the Hartree-Fock approach work well for transitional and deformed nuclei. Our NPA calculations using collective pairs with angular momenta 0, 2, and 4 (denoted by S D G pairs) reproduce the nuclear shape evolution in the N = 26 isotones, Ca 46 , Ti 48 , Cr 50 , and Fe 52 , and yield good agreement with full configuration-interaction calculations of low-lying states in medium-heavy transitional and deformed nuclei: Ti 44 – 48 , Cr 48 , Cr 50 , Fe 52 , Zn 60 – 64 , Ge 64 , 66 , Mo 84 , and Xe 108 – 112 . Finally, using the S D G I -pair approximation we describe low-lying states of Ba 112 , 114 , cases difficult to reach by conventional configuration-interaction methods.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Triaxiality and the nature of low-energy excitations in Ge 76

The deformation properties of the low-lying states in 76 Ge have been investigated following a safe energy Coulomb excitation measurement with the GRETINA tracking array and CHICO2 heavy-ion counter at the ATLAS accelerator facility at Argonne National Laboratory. A comprehensive set of transition and static E2 matrix elements were extracted from the measured differential Coulomb cross-sections, and compared with results of configuration interaction shell-model calculations and computations carried out within the framework of the generalized triaxial rotor model. The remarkable agreement between the calculated and experimental data supports a near-maximum triaxial deformation for the ground state of 76 Ge. Additionally, the degree of softness of the asymmetry in 76 Ge and 76 Se was investigated using rotational invariants generated from configuration interaction shell-model wave functions computed with the jj44b and JUN45 effective interactions. The resulting invariants are shown to be consistent with a stiff triaxial deformation in 76 Ge and a predominantly soft triaxial potential for 76 Se, in agreement with the conclusions of recent works by this collaboration.

59 ≤ A ≤ 89↗
DOE OSTI2019

Spin–Orbit Coupling Constants in Atoms and Ions of Transition Elements: Comparison of Effective Core Potentials, Model Core Potentials, and All-Electron Methods

The spin–orbit coupling constants (SOCC) in atoms and ions of the first- through third-row transition elements were calculated for the low-lying atomic states whose main electron configuration is [ n d] q ( q = 1–4 and 6–9, n = the principal quantum number), using four different approaches: (1) a nonrelativistic Hamiltonian used to construct multiconfiguration self-consistent field (MCSCF) wave functions utilizing effective core potentials and their associated basis sets within the framework of second-order configuration interaction (SOCI) to calculate spin–orbit couplings (SOC) using one-electron Breit–Pauli Hamiltonian (BPH), (2) a nonrelativistic Hamiltonian used to construct MCSCF wave functions utilizing model core potentials and their associated basis sets within the framework of SOCI to calculate SOC using the full BPH, (3) nonrelativistic and spin-independent relativistic Hamiltonians used to construct MCSCF wave functions utilizing all-electron (AE) basis sets within the framework of SOCI to calculate SOC using the full BPH, and (4) a relativistic Hamiltonian given by the exact two-component (X2C) transformation for construction of Kramers-restricted relativistic configuration interaction wave functions. In this investigation, these four approaches are referred to as ECP, MCP, AE, and X2C methods, respectively. The ECP, MCP, and AE methods are so-called two-step approaches (TSA), while the X2C method is a one-step approach (OSA). In the AE method, three different calculations—relativistic elimination of small components (RESC), third-order Douglas–Kroll–Hess (DKH3), and infinite-order two-component (IOTC) relativistic correction—were performed for the estimation of the scalar relativistic components in addition to those of the nonscalar relativistic (NSR) contributions. The calculated SOCC are compared to the available experimental data via the Landé interval rule. Although there are several exceptions, including states whose main configuration is [ n d] 5 , the average differences between the ECP and AE (IOTC) SOCC and between the ECP and the X2C SOCC are mostly less than 20%. The differences between the ECP and the experimental SOCC are even smaller. No serious discrepancy was found between the TSA and OSA predictions of SOCC for the first- and second-row transition elements in comparison to experiment. For atoms and ions of the third-row transition elements, the SOCC calculated through the Landé interval rule are not reliable. The low-energy spin-mixed (SM) states originating from a [5d]q configuration ( q = 2–4) have a larger energy lowering due to the SOC effects, in comparison with those for atoms and ions of the first- and second-row transition elements. For the spin-mixed (SM) states originating from a [5d]q configuration ( q = 6–8), the energy lowering of all 4 F 7/2 , 5 D 1 , and 5 D 3 states due to the SOC effects is smaller than those of the other SM states. Furthermore this difficulty, which also arises for the MCP, AE, and X2C (OSA) approaches, suggests that the LS-coupling scheme is inappropriate.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1991

Quantum mechanical calculations to chemical accuracy

The accuracy of current molecular-structure calculations is illustrated with examples of quantum mechanical solutions for chemical problems. Two approaches are considered: (1) the coupled-cluster singles and doubles (CCSD) with a perturbational estimate of the contribution of connected triple excitations, or CCDS(T); and (2) the multireference configuration-interaction (MRCI) approach to the correlation problem. The MRCI approach gains greater applicability by means of size-extensive modifications such as the averaged-coupled pair functional approach. The examples of solutions to chemical problems include those for C-H bond energies, the vibrational frequencies of O3, identifying the ground state of Al2 and Si2, and the Lewis-Rayleigh afterglow and the Hermann IR system of N2. Accurate molecular-wave functions can be derived from a combination of basis-set saturation studies and full configuration-interaction calculations.

Bauschlicher, Charles W., Jr.↗
DOE OSTI2022

Nucleon-pair truncation of the shell model for medium-heavy nuclei

Background: Establishing computationally tractable models of atomic nuclei is a long-time goal of nuclear structure physics. A flexible framework which easily includes excited states and many-body correlations is the configuration-interaction shell model (SM), but the exponential growth of the basis means one needs an efficient truncation scheme, ideally one that includes both deformation and pairing correlations. Purpose: Here, we propose an efficient truncation scheme of the SM: starting from a pair condensate variationally defined by Hartree-Fock single-particle states and the particle-number conserved Bardeen-Cooper-Schrieffer (NBCS) approximation, we carry out projection of states with good angular momentum. Methods: After generating Hartree-Fock single-particle states with Kramers degeneracy in a SM space, we optimize the pair amplitudes in the NBCS by minimizing the energy, and then use linear algebra projection (LAP) of states with good angular momentum. Both NBCS and LAP are computationally fast. Results: Our calculations yield good agreement with full configuration-interaction SM calculations for low-lying states of transitional and rotational nuclei with axially symmetric and triaxial deformation in medium- and heavy-mass regions: 44,46,48 Ti, 48,50 Cr, 52 Fe, 60,62,64 Zn, 66,68 Ge, 68 Se, and 108,110 Xe. We predict low-lying states of 112–114 Ba and 116–120 Ce, nuclei difficult to reach by large-scale SM calculations. Conclusions: Both pair correlation and the configuration mixing between different intrinsic states play a key role in reproducing collectivity and shape coexistence, demonstrating the utility of this truncation scheme of the SM to study transitional and deformed nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Degenerate coupled-cluster theory

A size-extensive, converging, black-box, ab initio coupled-cluster (ΔCC) ansatz is introduced that computes the energies and wave functions of states from any degenerate or nondegenerate Slater-determinant references with any numbers of α- and β-spin electrons, any patterns of orbital occupancy, any spin multiplicities, and any spatial symmetries. For a nondegenerate reference, it reduces to the single-reference coupled-cluster ansatz. For a degenerate multireference, it is a natural coupled-cluster extension of degenerate Møller–Plesset perturbation (ΔMP) theory. For ionized and electron-attached references, it is a coupled-cluster Green’s function, although the present theory is convergent toward the full-configuration-interaction limits, while the Feynman–Dyson many-body Green’s function (MBGF) theory generally is not. Its single-excitation instance is a projection Hartree–Fock theory as per the Thouless theorem, which may be useful for core ionizations, high-spin states, and possibly electron affinities. Additionally, a new multireference coupled-cluster theory for a general model space is developed. This quasidegenerate coupled-cluster (QCC) theory is exactly converging, but not black-box, and intended for strong correlation. Determinant-based, general-order algorithms of ΔCC and QCC theories are implemented and compared with configuration-interaction (CI) and equation-of-motion coupled-cluster (EOM-CC) theories through octuple excitations and with ΔMP and MBGF theories up to the nineteenth order. An algebraic, optimal-scaling algorithm of the ΔCC theory is computer-synthesized at the levels of single excitations (ΔCCS) and of single and double excitations (ΔCCSD). As a result, the order of performance is QCC ≈ ΔCC > EOM-CC > CI at the same order or QCC ≈ ΔCC > ΔMP > MBGF at the same cost scaling.

Hirata, So [University of Illinois at Urbana-Champ↗
DOE OSTI2024

Light-induced electron dynamics of molecules in cavities: comparison of model Hamiltonians

The rapidly expanding field of polaritonic chemistry requires accurate theoretical simulations to understand new phenomena at the atomic scale. Computing the optoelectronic properties of molecules using established electronic structure methods is a careful balance of accuracy and computational expense, and expanding these methods to quantum electrodynamics to describe coupled cavity-molecule systems is an active topic of development. Key to these methods are the Hamiltonian operators representing the photon cavity modes. The recently introduced quantum electrodynamics time-dependent configuration interaction (QED-TDCI) method allows for the combination of electron dynamics simulations with quantum electrodynamics, enabling the simulation of time-dependent optoelectronic properties of cavity-molecule systems. Using this method, a comparison of two many-state QED Hamiltonians—the Pauli-Fierz and quantum Rabi model Hamiltonians—is presented, with a particular focus on time-dependent properties in applied electric fields.

Peyton, Benjamin G. (ORCID:0000000163190751)↗
DOE OSTI2016

An improved quasi-diabatic representation of the 1, 2, 3 1 A coupled adiabatic potential energy surfaces of phenol in the full 33 internal coordinates

In a previous project we constructed a quasi-diabatic representation, H d , of the 1, 2, 3 1 A adiabatic states of phenol from high level multireference single and double excitation configuration interaction electronic structure data, energies, energy gradients, and derivative couplings. That H d accurately describes surface minima, saddle points, and also regions of strong nonadiabatic interactions, reproducing the locus of conical intersection seams and the coordinate dependence of the derivative couplings. The present work determines the accuracy of H d for describing phenol photodissociation. Additionally, we demonstrate that a modest energetic shift of two diabats yields a quantifiably more accurate H d compared with experimental energetics. The analysis shows that in favorable circumstances it is possible to use single point energies obtained from the most reliable electronic structure methods available, including methods for which the energy gradients and derivative couplings are not available, to improve the quality of a global representation of several coupled potential energy surfaces. Our data indicate an alternative interpretation of kinetic energy release measurements near λ phot ~ 248 nm.

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

Time-Dependent Complete Active Space Embedded in Polarizable Force Field

Electron correlation and environmental effects play important roles in electron dynamics and spectroscopic observables of chemical systems in condensed phase. In this paper, we present a time-dependent complete active space configuration interaction (TD-CASCI) approach embedded in a polaraizable force filed, MMPol. The present implementation of TD-CASCI/MMPol utilizes a direct matrix-vector contraction, allowing studies of large systems. This scheme is used to study the solvatochromic shift of coumarin 153 in methanol. The TD-CASCI/MMPol approach captures the double excitation character in the excited state wave function and accurately predicts the solvatochromic red-shift of coumarin 153 dye within the experimental range, outperforming linear response time-dependent density functional theory. The effect of using different reference orbitals for the TD-CASCI/MMPol simulation is also investigated, highlighting the need for an unbiased treatment of all electronic states in the energy range of interest.

Liu, Hongbin↗
DOE OSTI2020

Resource-Efficient Chemistry on Quantum Computers with the Variational Quantum Eigensolver and The Double Unitary Coupled-Cluster approach

Applications of quantum simulation algorithms to obtain electronic energies of molecules on noisy intermediate-scale quantum (NISQ) devices require careful consideration of resources describing the complex electron correlation effects. In modeling second-quantized problems, the biggest challenge confronted is that the number of qubits scales linearly with the size of molecular basis. This poses a significant limitation on the size of the basis sets and the number of correlated electrons included in quantum simulations of chemical processes. To address this issue and to enable more realistic simulations on NISQ computers, we employ the double unitary coupled-cluster (DUCC) method to effectively downfold correlation effects into the reduced-size orbital space, commonly referred to as the active space. Using downfolding techniques, we demonstrate that properly constructed effective Hamiltonians can capture the effect of the whole orbital space in small-size active spaces. Combining the downfolding pre-processing technique with the Variational Quantum Eigensolver, we solve for the ground-state energy of H2 and Li2 in the cc-pVTZ basis using the DUCC-reduced active spaces. We compare these results to full configuration-interaction and high-level coupled-cluster reference calculations.

quantum computing, variational quantum solver, cou↗
DOE OSTI2016

Ab Initio Reaction Kinetics of CH 3 O$\dot{C}$(=O) and $\dot{C}$H 2 OC(=O)H Radicals

The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3O$\dot{C}$(=O)) and (formyloxy)methyl radical ($\dot{C}$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$\dot{C}$(=O) to $\dot{C}$H3 and CO2 is predicted to be much faster than dissociating to CH3$\dot{O}$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$\dot{C}$(=O) and $\dot{C}$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$\dot{O}$ removal mechanisms under atmospheric conditions, the reaction kinetics of CH3$\dot{O}$ + CO was also studied along the PES of CH3O$\dot{C}$(=O); the resulting kinetics predictions are in remarkable agreement with experiments.

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

Radiative rates for E1, E2, M1, and M2 transitions in S-like to F-like tungsten ions (W LIX to W LXVI)

Calculations of energy levels, radiative rates and lifetimes are reported for eight ions of tungsten, i.e. S-like (W LIX) to F-like (W LXVI). A large number of levels have been considered for each ion and extensive configuration interaction has been included among a range of configurations. For the calculations, the general-purpose relativistic atomic structure package (grasp) has been adopted, and radiative rates (as well as oscillator strengths and line strengths) are listed for all E1, E2, M1, and M2 transitions of the ions. Comparisons have been made with earlier available experimental and theoretical energies, although these are limited to only a few levels for most ions. Therefore for additional accuracy assessments, particularly for energy levels, analogous calculations have been performed with the flexible atomic code (fac).

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗