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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Local Pair Natural Orbital-Based Coupled-Cluster Theory through Full Quadruples (DLPNO–CCSDTQ)

In this work, we implement a local pair natural orbitalbased coupled-cluster method through the full treatment of quadruple excitations (CCSDTQ). The domain-based local pair natural orbital (DLPNO) approach, which has successfully been applied to lower levels of coupled-cluster theory, is utilized in our algorithm, and thus our algorithm is called DLPNO-CCSDTQ. For simplicity in the working equations and in the implementation, we t 1 -dress the twoelectron integrals as well as Fock matrix elements. Our method can recover CCSDTQ-CCSDT and CCSDTQ-CCSDT(Q) energy differences on the order of 0.01−0.05 kcal mol −1 , even at a loose quadruples natural orbital (QNO) occupation number cutoff of 3.33 × 10 −6 . To highlight the capabilities of our code and its potential future applications, we showcase computations that would be intractable with canonical CCSDTQ, such as the benzene dimer, (H 2 O) 17 , and adamantane. With sufficient computing resources, computations up to 15 heavy atoms (40 atoms overall) may be feasible for fully bonded 3D systems.

Cluster chemistry↗
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↗
NASA NTRS1988

Symmetry and equivalence restrictions in electronic structure calculations

A simple method for obtaining MCSCF orbitals and CI natural orbitals adapted to degenerate point groups, with full symmetry and equivalnece restrictions, is described. Among several advantages accruing from this method are the ability to perform atomic SCF calculations on states for which the SCF energy expression cannot be written in terms of Coulomb and exchange integrals over real orbitals, and the generation of symmetry-adapted atomic natural orbitals for use in a recently proposed method for basis set contraction.

Bauschlicher, Charles W., Jr.↗
DOE OSTI2026

One-Body Properties and Their Perturbative Accuracy with Aufbau Suppressed Coupled Cluster Theory

In this work we derived and implemented the calculation of the one-body reduced density matrix for Aufbau suppressed coupled cluster theory, from which excited state natural orbitals and one-body properties, like atomic populations and dipole moments, are obtained. We utilized the natural orbitals to refine the ASCC solution for simple valence and Rydberg systems, exploring the process of repeatedly solving the ASCC equations in successive natural orbital bases to achieve independence from the starting molecular orbitals. For dipole moments in small molecules where high-level comparison data is available, we find that the accuracy of ASCC essentially matches that of linear response and equation-of-motion coupled cluster as long as care is taken to preserve the response's perturbative completeness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Analytical and experimental vibration studies of a 1/8-scale shuttle orbiter

Natural frequencies and mode shapes for four symmetric vibration modes and four antisymmetric modes are compared with predictions based on NASTRAN finite-element analyses. Initial predictions gave poor agreement with test data; an extensive investigation revealed that the major factors influencing agreement were out-of-plane imperfections in fuselage panels and a soft fin-fuselage connection. Computations with a more refined analysis indicated satisfactory frequency predictions for all modes studied, within 11 percent of experimental values.

Pinson, L. D.↗
DOE OSTI2020

Quantum chemical topology and natural bond orbital analysis of M–O covalency in M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np)

Covalency is complex yet central to our understanding of chemical bonding, particularly in the actinide series. In this work, we assess covalency in a series of isostructural d and f transition element compounds M(OC 6 H 5 ) 4 (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density functional theory in conjunction with the Natural Bond Orbital (NBO), quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) approaches. The IQA exchange–correlation covalency metric is evaluated for the first time for actinides other than uranium, in order to assess its applicability in the 5f series. It is found to have excellent correlation with NBO and QTAIM covalency metrics, making it a promising addition to the computational toolkit for analysing metal–ligand bonding. Our range of metrics agree that the actinide-oxygen bonds are the most covalent of the elements studied, with those of the heavier group 4 elements the least. Within the early actinide series, Th stands apart from the other three elements considered, being consistently the least covalent.

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

Explicitly correlated coupled cluster method for accurate treatment of open-shell molecules with hundreds of atoms

We present a near-linear scaling formulation of the explicitly correlated coupled-cluster singles and doubles with the perturbative triples method [CCSD(T)F12¯] for high-spin states of open-shell species. The approach is based on the conventional open-shell CCSD formalism [M. Saitow et al., J. Chem. Phys. 146, 164105 (2017)] utilizing the domain local pair-natural orbitals (DLPNO) framework. The use of spin-independent set of pair-natural orbitals ensures exact agreement with the closed-shell formalism reported previously, with only marginally impact on the cost (e.g., the open-shell formalism is only 1.5 times slower than the closed-shell counterpart for the C160H322 n-alkane, with the measured size complexity of ≈1.2). Evaluation of coupled-cluster energies near the complete-basis-set (CBS) limit for open-shell systems with more than 550 atoms and 5000 basis functions is feasible on a single multi-core computer in less than 3 days. The aug-cc-pVTZ DLPNO-CCSD(T)F12¯ contribution to the heat of formation for the 50 largest molecules among the 348 core combustion species benchmark set [J. Klippenstein et al., J. Phys. Chem. A 121, 6580–6602 (2017)] had root-mean-square deviation (RMSD) from the extrapolated CBS CCSD(T) reference values of 0.3 kcal/mol. For a more challenging set of 50 reactions involving small closed- and open-shell molecules [G. Knizia et al., J. Chem. Phys. 130, 054104 (2009)], the aug-cc-pVQ(+d)Z DLPNO-CCSD(T)F12¯ yielded a RMSD of ∼0.4 kcal/mol with respect to the CBS CCSD(T) estimate.

Kumar, Ashutosh (ORCID:0000000175896030)↗
NASA NTRS1980

On the 3d2 4s2, 3d3 4s1, and 3d4 states of Ti

The energies of the 3F (3d2 4s2), 5F (3d3 4s1) and 5D (3d4) states of Ti are investigated on the basis of MCSCF and CI calculations. Following SCF calculations using a basis set including the primitive set of Wachters (1970) and the diffuse d function of Hay (1977), four full-electron CI calculations involving the 3d and 4s electrons were performed to obtain the natural orbitals, and the full CI calculations were repeated. MCSCF calculations then performed using the most important configurations of the natural orbital basis are found to be in agreement with those of Dunning (1980), but to differ from CI results. CI(SD) calculations including single and double excitations from the MCSCF reference are found to be in agreement with the full CI but differ from experimental energy separations. Further calculations reveal that Dunning's MCSCF description is an oversimplication of the problem, and that the 5F-5D separation at the CI(SD) level is in good agreement with experiment for all basis sets but the 3F state is too low relative to the 5F and 5D states.

Bauschlicher, C. W., Jr.↗
DOE OSTI2020

Accelerating the convergence of auxiliary-field quantum Monte Carlo in solids with optimized Gaussian basis sets

We investigate the use of optimized correlation-consistent Gaussian basis sets for the study of insulating solids with auxiliary-field quantum Monte Carlo (AFQMC). The exponents of the basis set are optimized through the minimization of the second-order Møller–Plesset perturbation theory (MP2) energy in a small unit cell of the solid. We compare against other alternative basis sets proposed in the literature, namely, calculations in the Kohn–Sham basis and in the natural orbitals of an MP2 calculation. We find that our optimized basis sets accelerate the convergence of the AFQMC correlation energy compared to a Kohn–Sham basis and offer similar convergence to MP2 natural orbitals at a fraction of the cost needed to generate them. We also suggest the use of an improved, method independent, MP2-based basis set correction that significantly reduces the required basis set sizes needed to converge the correlation energy. With these developments, we study the relative performance of these basis sets in LiH, Si, and MgO and determine that our optimized basis sets yield the most consistent results as a function of volume. Using these optimized basis sets, we systematically converge the AFQMC calculations to the complete basis set and thermodynamic limit and find excellent agreement with experiment for the systems studied. Although we focus on AFQMC, our basis set generation procedure is independent of the subsequent correlated wavefunction method used.

Morales, Miguel A. (ORCID:0000000263893067)↗
DOE OSTI2021

Coupled cluster benchmarks of large noncovalent complexes: The L7 dataset as well as DNA–ellipticine and buckycatcher–fullerene

In this work, benchmark binding energies for dispersion-bound complexes in the L7 dataset, the DNA–ellipticine intercalation complex, and the buckycatcher–C60 complex with 120 heavy atoms using a focal-point method based on the canonical form of second-order Møller−Plesset theory (MP2) and the domain based local pair natural orbital scheme for the coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set (CBS) limit are reported. This work allows for increased confidence given the agreement with respect to values recently obtained using the local natural orbital CCSD(T) for L7 and the canonical CCSD(T)/CBS result for the coronene dimer (C2C2PD). Therefore, these results can be considered pushing the CCSD(T)/CBS binding benchmark to the hundred-atom scale. The disagreements between the two state-of-the-art methods, CCSD(T) and fixed-node diffusion Monte Carlo, are substantial with at least 2.0 (∼10%), 1.9 (∼5%), and 10.3 kcal/mol (∼25%) differences for C2C2PD in L7, DNA–ellipticine, and buckycatcher–C60, respectively. Such sizable discrepancy above “chemical accuracy” for large noncovalent complexes indicates how challenging it is to obtain benchmark binding interactions for systems beyond small molecules, although the three up-to-date density functionals, PBE0+D4, ωB97M-V, and B97M-V, agree better with CCSD(T) for these large systems. In addition to reporting these values, different basis sets and various CBS extrapolation parameters for Hartree–Fock and MP2 correlation energies were tested for the first time in large noncovalent complexes with the goal of providing some indications toward optimal cost effective routes to approach the CBS limit without substantial loss in quality.

Ballesteros, Francisco (ORCID:0000000325732307)↗
NASA NTRS1995

Natural and orbital debris particles on LDEF's trailing and forward-facing surfaces

Approximately 1000 impact craters on the Chemistry of Meteoroid Experiment (CME) have been analyzed by means of Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Analysis (EDXA) to determine the compositional make-up of projectile residues. This report completes our systematic survey of gold and aluminum surfaces exposed at the trailing-edge (A03) and forward-facing (A11) LDEF sites, respectively. The major categories for the projectile residues were (1) natural, with diverse subgroups such as chondritic, monomineralic silicates, and sulfides, and (2) man made, that were classified into aluminum (metallic or oxide) and miscellaneous materials (such as stainless steel, paint flakes, etc). On CME gold collectors on LDEF's trailing edge approximately 11 percent of all craters greater than 100 micron in diameter were due to man-made debris, the majority (8.6 percent) caused by pure aluminum, approximately 31.4 percent were due to cosmic dust, while the remaining 58 percent were indeterminate via the analytical techniques utilized in this study. The aluminum surfaces located at the A11 forward-facing site did not permit analysis of aluminum impactors, but approximately 9.4 percent of all craters were demonstratably caused by miscellaneous debris materials and approximately 39.2 percent were the result of natural particles, leaving approximately 50 percent which were indeterminate. Model considerations and calculations are presented that focus on the crater-production rates for features greater than 100 micron in diameter, and on assigning the intermediate crater population to man-made or natural particles. An enhancement factor of 6 in the crater-production rate of natural impactors for the 'forward-facing' versus the 'trailing-edge' CME collectors was found to best explain all observations (i.e., total crater number(s), as well as their computational characteristics). Enhancement factors of 10 and 4 are either too high or too low. It is also suggested that approximately 45 percent of all craters greater than 100 micron in diameter are caused by man-made impactors on the A11 surfaces. This makes the production rate for craters greater than 100 micron in diameter, resulting from orbital debris, a factor of 40 higher on the forward-facing sides as opposed to the trailing-edge direction.

Hoerz, Friedrich↗
DOE OSTI2021

Reducing Qubit Requirements while Maintaining Numerical Precision for the Variational Quantum Eigensolver: A Basis-Set-Free Approach

We present a basis-set-free approach to the variational quantum eigensolver using an adaptive representation of the spatial part of molecular wave functions.Our approach directly determines system-specific representations of qubit Hamiltonians while fully omitting globally defined basis sets. In this work, we use directly determined pair-natural orbitals on the level of second-order perturbation theory. This results in compact qubit Hamiltonians with high numerical accuracy. We demonstrate initial applications with compact Hamiltonians on up to 22 qubits where conventional representation would for the same systems require 40–100 or more qubits. Here, we further demonstrate reductions in the quantum circuits through the structure ofthe pair-natural orbitals.

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

Collective Nature of Orbital Excitations in Layered Cuprates in the Absence of Apical Oxygens

Here, we have investigated the 3 d orbital excitations in CaCuO 2 (CCO), Nd 2 CuO 4 (NCO), and La 2 CuO 4 (LCO) using high-resolution resonant inelastic x-ray scattering. In LCO they behave as well-localized excitations, similarly to several other cuprates. On the contrary, in CCO and NCO the d xy orbital clearly disperse, pointing to a collective character of this excitation (orbiton) in compounds without apical oxygen. We ascribe the origin of the dispersion as stemming from a substantial next-nearest-neighbor (NNN) orbital superexchange. Such an exchange leads to the liberation of orbiton from its coupling to magnons, which is associated with the orbiton hopping between nearest neighbor copper sites. Finally, we show that the exceptionally large NNN orbital superexchange can be traced back to the absence of apical oxygens suppressing the charge transfer energy.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Linear-Scaling Asymmetric Triples Correction through the Solution of the DLPNO–CCSD Lambda Equations: DLPNO–CCSD(T) Λ

In this research, we derive equations for solving for the stationary points of the DLPNO–CCSD Lagrangian, in the t 1 -transformed formalism introduced earlier and as currently implemented in the P SI 4 quantum chemistry software package. These lambda equations in the local pair natural orbital basis allow for the evaluation of CCSD(T) Λ energetics with linear-scaling computational effort, also known as the asymmetric triples correction. This DLPNO–CCSD(T) Λ method allows for accurate triples contributions to be computed for larger molecules, especially in cases that CCSD(T) is known to be insufficient, such as with multireference systems and bond-breaking systems. We showcase the accuracy of our code on reaction energies, barrier heights, and noncovalent interaction energies. Also showcased are the capabilities of our code by evaluating DLPNO–CCSD(T) Λ energetics on large noncovalent dimers up to 112 atoms, as well as a rhodium catalyst complex containing 66 atoms.

Cluster chemistry↗
NASA NTRS1993

A simultaneous estimation of the mass of Mars and its natural satellites, Phobos and Deimos, from the orbital perturbations on the Mariner 9, Viking 1, and Viking 2 orbiters

The natural satellites of Mars, Phobos and Deimos, caused perturbations on the orbits of the Mariner 9, and the Viking spacecraft that were used to estimate the satellite masses. The Viking spacecraft were specifically targeted to make close flybys (within a few hundred kilometers) of Phobos in February 1977 and of Deimos in October 1977. These close encounters were used to estimate the moon's gravitational constant, GM (the universal constant of gravitation multiplied by the satellite mass). However, the Viking and Mariner 9 spacecraft made numerous flybys of Phobos and Deimos at distances of a few thousand kilometers. The tracking data from these more 'distant' encounters were processed to estimate the masses of Mars, Phobos, and Deimos.

Lemoine, F. G.↗
DOE OSTI2025

Hetero-Orbital Two-Component Fractional Quantum Hall States in Bilayer Graphene

A two-dimensional electron system exposed to a strong magnetic field produces a plethora of strongly interacting fractional quantum Hall (FQH) states, the complex topological orders of which are revealed through exotic emergent particles, such as composite fermions, and fractionally charged Abelian and non-Abelian anyons. Much insight has been gained by the study of multicomponent FQH states, where spin and pseudospin indices of the electron contribute additional correlation. Traditional multicomponent FQH states develop in situations where the components share the same orbital states and the resulting interactions are pseudospin independent; this homo-orbital nature is also crucial to their theoretical understanding. Here, we study “hetero-orbital” two-component FQH states, in which the orbital index is part of the pseudospin, rendering the multicomponent interactions strongly SU(2) anisotropic in the pseudospin space. Such states, obtained in bilayer graphene at the isospin transition between 𝑁 = 0 and 𝑁 = 1 electron Landau levels, are markedly different from previous homo-orbital two-component FQH states. In particular, we observe strikingly different behaviors for the parallel-vortex and reverse-vortex attachment composite fermion states, and an anomalously strong two-component 2/5 state over a wide range of magnetic field before it abruptly disappears at a high field. Our findings, combined with detailed theoretical calculations, reveal the surprising robustness of the hetero-orbital FQH effects, significantly enriching our understanding of FQH physics in this novel regime.

Bilayer graphene↗
NASA NTRS1986

Large manned systems/environment interactions in Low Earth Orbit (LEO)

With the advent of the NASA Space Transportation System, regular flights of a large manned spacecraft, the Space Shuttle Orbiter, became a reality. From the earliest mission containing space science instruments as a payload on the third flight of the Orbiter (STS-3), it became apparent that the disturbance caused by the interaction of this orbiting system with the low Earth orbit (LEO) environment resulted in adverse conditions for the performance of scientific observations of the Orbiter natural environment and for certain high sensitivity optical observations. The interaction of the Space Shuttle Orbiter system can be divided into two parts, the structure-environment interaction, and the outgas cloud-environment interaction. These interaction are briefly discussed.

Raitt, W. J.↗