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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Magnetic excitations from the hexagonal spin clusters in the 𝑆 = $\frac{1}{2}$ distorted honeycomb lattice antiferromagnet Cu 2 ⁢(pymca)⁢ 3 ⁢(ClO 4 )

Cu 2 ⁢(pymca) ⁢3 (ClO 4 ) (pymca: pyrimidine-2-carboxylate) consists of a slightly distorted honeycomb lattice of Cu 2+ spins, which shows no long-range magnetic order down to 0.6 K. A magnetization study revealed 1/3 and 2/3 plateau phases [A. Okutani et al., J. Phys. Soc. Jpn. 88, 013703 (2019)], which is not expected for regular honeycomb antiferromagnets. Inelastic neutron scattering experiments were performed using a powder sample to investigate the exchange interactions of this material. The spin excitations from the singlet ground state to the first three triplet states, predicted from the antiferromagnetic hexagonal spin cluster interacting with 3.9 meV, were observed. Using the exact diagonalization methods, the intercluster coupling was estimated from the excitation peak width to be about 20% of the intracluster interaction, which is consistent with the previously reported value. Finally, our exchange path model explains the anisotropic exchange interactions in the distorted honeycomb plane.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1995

Characterization of the Minimum Energy Paths and Energetics for the Reaction of Vinylidene with Acetylene

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinyl-acetylene and for a number of isomers of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinyl-acetylene.

Walch, Stephen P.↗
NASA NTRS1995

Characterization of the Minimum Energy Paths and Energetics for the reaction of Vinylidene with Acetylene

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinylacetylene and for a number of isomers Of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinylacetylene.

Walch, Stephen P.↗
DOE OSTI2023

Molecular Symmetry in VQE: A Dual Approach for Trapped-Ion Simulations of Benzene

Understanding complex chemical systems—such as biomolecules, catalysts, and novel materials—is a central goal of quantum simulations. Near-term strategies hinge on the use of variational quantum eigensolver (VQE) algorithms combined with a suitable ansatz. However, straightforward application of many chemically-inspired ansatze yields prohibitively deep circuits. In this work, we employ several circuit optimization methods tailored for trapped-ion quantum devices to enhance the feasibility of intricate chemical simulations. The techniques aim to lessen the depth of the unitary coupled cluster with singles and doubles (uCCSD) ansatz's circuit compilation, a considerable challenge on current noisy quantum devices. Furthermore, we use symmetry-inspired classical post-selection methods to further refine the outcomes and minimize errors in energy measurements, without adding quantum overhead. Our strategies encompass optimal mapping from orbital to qubit, term reordering to minimize entangling gates, and the exploitation of molecular spin and point group symmetry to eliminate redundant parameters. The inclusion of error mitigation via post-selection based on known molecular symmetries improves the results to near milli-Hartree accuracy. These methods, when applied to a benzene molecule simulation, enabled the construction of an 8-qubit circuit with 69 two-qubit entangling operations, pushing the limits for variational quantum eigensolver (VQE) circuits executed on quantum hardware to date. 1 1 This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-000R22725 with the US Department of Energy (DOE). The publisher acknowledges the US government license to provide public access under the DOE Public Access Plan(https://energy.gov/doe-public-access-plan).

Goings, Joshua↗
NASA NTRS1989

A diagnostic for determining the quality of single-reference electron correlation methods

It was recently proposed that the Euclidian norm of the t sub 1 vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appropriate. This diagnostic, T sub 1, is defined for use with self consistent field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T sub 1 is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of nondynamical electron correlation and is far superior to C sub 0 from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T sub 1 (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.

Lee, Timothy J.↗
NASA NTRS1989

A diagnostic for determining the quality of single-reference electron correlation methods

It was recently proposed that the Euclidian norm of the t(sub 1) vector of the coupled cluster wave function (normalized by the number of electrons included in the correlation procedure) could be used to determine whether a single-reference-based electron correlation procedure is appopriate. This diagnostic, T(sub 1) is defined for use with self-consistent-field molecular orbitals and is invariant to the same orbital rotations as the coupled cluster energy. T(sub 1) is investigated for several different chemical systems which exhibit a range of multireference behavior, and is shown to be an excellent measure of the importance of non-dynamical electron correlation and is far superior to C(sub 0) from a singles and doubles configuration interaction wave function. It is further suggested that when the aim is to recover a large fraction of the dynamical electron correlation energy, a large T(sub 1) (i.e., greater than 0.02) probably indicates the need for a multireference electron correlation procedure.

Lee, Timothy J.↗
DOE OSTI2025

Perspective on Many-Body Methods for Molecular Polaritonic Systems

Recent advances in strong light–matter interactions have revealed a wealth of new physical phenomena in molecules embedded in optical cavities, including modified chemical reactivity, altered excitation spectra, and novel quantum correlations. To describe these effects from first-principles, the field of ab initio quantum electrodynamics (QED) has emerged as a compelling extension of quantum chemistry that treats electronic and photonic degrees of freedom on equal footing. In this Perspective, we review the growing landscape of many-body QED methods, including Hartree–Fock, density functional theory (QEDFT), time-dependent DFT (QED-TDDFT), configuration interaction (QED-CI), complete active space (QED-CASSCF), coupled cluster (QED-CC), quantum Monte Carlo (QED-QMC), and density matrix renormalization group (QED-DMRG), highlighting recent developments and implementations. We further explore real-time methods, gradient and Hessian formalisms, and the integration of nonadiabatic nuclear dynamics. Applications range from benchmark simulations of polaritonic chemistry to quantum simulations on emerging quantum hardware. We conclude by outlining future directions for theory development and interdisciplinary efforts at the interface of quantum chemistry, condensed matter, and quantum optics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

N 5 -Scaling Excited-State-Specific Perturbation Theory

In this paper, we show that by working in a basis similar to that of the natural transition orbitals and using a modified zeroth-order Hamiltonian, the cost of a recently introduced perturbative correction to excited-state mean field theory can be reduced from seventh to fifth order in the system size. The (occupied) 2 (virtual) 3 asymptotic scaling matches that of ground-state second-order Møller-Plesset theory but with a significantly higher prefactor because the bottleneck is iterative: it appears in the Krylov-subspace-based solution of the linear equation that yields the first-order wave function. Here, we discuss the details of the modified zeroth-order Hamiltonian we use to reduce the cost and the automatic code generation process we used to derive and verify the cost scaling of the different terms. Overall, we find that our modifications have little impact on the method's accuracy, which remains competitive with singles and doubles equation-of-motion coupled cluster.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Performance of wave function and Green's function methods for non-equilibrium many-body dynamics

Theoretical descriptions of the non-equilibrium dynamics of quantum many-body systems essentially employ either (i) explicit treatments, relying on the truncation of the expansion of the many-body wave function, (ii) compressed representations of the many-body wave function, or (iii) evolution of an effective (downfolded) representation through Green's functions. In this work, we select representative cases of each of the methods and address how these complementary approaches capture the dynamics driven by intense field perturbations to non-equilibrium states. Under strong driving, the systems are characterized by strong entanglement of the single-particle density matrix and natural populations approaching those of a strongly interacting equilibrium system. We generate a representative set of results that are numerically exact and form a basis for a critical comparison of the distinct families of methods. We demonstrate that the compressed formulation based on similarity-transformed Hamiltonians (coupled-cluster approach) is practically exact in weak fields and, hence, weakly or moderately correlated systems. Coupled cluster, however, struggles for strong driving fields, under which the system exhibits strongly correlated behavior, as measured by the von Neumann entropy of the single-particle density matrix. The dynamics predicted by Green's functions in the (widely popular) G W approximation are less accurate, but improve significantly upon the mean-field results in the strongly driven regime. Published by the American Physical Society 2025

Reeves, Cian C. (ORCID:0009000642581845)↗
DOE OSTI2025

Systematic improvement of trial states in phaseless auxiliary-field quantum Monte Carlo

We extend the use of coupled cluster (CC) trial states in the phaseless auxiliary-field quantum Monte Carlo (AFQMC) method beyond single and double excitations to include both triple and quadruple excitations. With this AFQMC/CC hierarchy, we are able to systematically benchmark the method's performance on molecular systems as the quality of the trial is improved. Our results show that the phaseless AFQMC energy improves systematically and is typically significantly more accurate than the energy of the underlying trial state. However, the relative improvement compared to the trial CC energy decreases as we ascend the CC hierarchy. As the CC wavefunction is usually further approximated when used as an AFQMC trial, we also explore the relationship between the components of the CC wavefunction and the resulting AFQMC/CC error. Our results suggest that improving the representation of the CC wave function in the AFQMC trial does not always lower the bias even when it increases the fidelity of the trial with the exact ground state.

Chemical Physics (physics.chem-ph)↗
DOE OSTI2025

Ultrafast Correlation Energy Estimator

A virtually no-cost method is proposed that can compute the correlation energies of general, covalently bonded, organic, and inorganic molecules (including conjugated π-electron systems) with a well-defined dominant Lewis structure at the accuracy of 99.5% of the near-exact values determined by the coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] in the complete-basis-set (CBS) limit. This Correlation Energy Per Bond (CEPB) method assigns a partial correlation energy to each bond type (characterized by the identities of the two atoms forming the bond and its integer bond order) and to a lone pair, regardless of the bond length, bond angle, sp-hybridization, π-electron conjugation, ionicity, noncovalent interactions, etc. At its current stage, the method is mainly suitable for near-equilibrium geometries. The correlation energies per bond are determined by a fit to the CCSD(T)/CBS benchmarks. It can neither improve the equilibrium structures nor discern conformers or positional isomers, yet its accuracy for reaction energies rivals that of the second-order Møller–Plesset perturbation theory, which is far more expensive. Its promising performance underscores the possibility that surprisingly compact, chemically intuitive molecular fragments exist into which correlation energies can be partitioned, leading to various ultrafast correlation-energy estimators tailored to different purposes.

Binding energy↗
DOE OSTI2020

Giant Wilson loops and AdS 2 /dCFT 1

The 1/2-BPS Wilson loop in N = 4 supersymmetric Yang-Mills theory is an important and well-studied example of conformal defect. In particular, much work has been done for the correlation functions of operator insertions on the Wilson loop in the fundamental representation. In this paper, we extend such analyses to Wilson loops in the large-rank symmetric and antisymmetric representations, which correspond to probe D3 and D5 branes with AdS 2 × S 2 and AdS 2 × S 4 worldvolume geometries, ending at the AdS 5 boundary along a one-dimensional contour. We first compute the correlation functions of protected scalar insertions from supersymmetric localization, and obtain a representation in terms of multiple integrals that are similar to the eigenvalue integrals of the random matrix, but with important differences. Using ideas from the Fermi Gas formalism and the Clustering method, we evaluate their large N limit exactly as a function of the ’t Hooft coupling. The results are given by simple integrals of polynomials that resemble the Q-functions of the Quantum Spectral Curve, with integration measures depending on the number of insertions. Next, we study the correlation functions of fluctuations on the probe D3 and D5 branes in AdS. We compute a selection of three- and four-point functions from perturbation theory on the D-branes, and show that they agree with the results of localization when restricted to supersymmetric kinematics. We also explain how the difference of the internal geometries of the D3 and D5 branes manifests itself in the localization computation.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Evaluation of phase change thermal storage in a cascade heat pump

Here this study proposes a low-global warming potential cascade heat pump system with integrated phase change material (PCM) for combined space heating and cooling. PCM is embedded in the intermediate heat exchanger that couples an outdoor R290 refrigerant circuit and an indoor CO 2 circuit. We used a clustering method to develop seasonally representative load and ambient temperature profiles for residential buildings in Minneapolis, Minnesota. We simulated the system peak shaving performance on the selected representative days, assuming three different PCM options including ice (0 °C), tetradecane (5.6 °C), and a commercially available PCM, SP9 (10.5 °C). The baseline was the same cascade system without thermal storage. We investigated the effect of both thermal energy storage capacity (kWh th ) and PCM transition temperature on system performance. The results show that higher thermal energy storage capacity shaves more electric energy until it reaches a maximum value set by the load characteristics of the building. SP9, with the highest transition temperature, shaves the most electric energy, while ice shaves the least. Moreover, ice has the highest charging cost, especially in the cooling season when the outdoor circuit has to operate at an evaporating temperature lower than 0 °C to make ice. Our results show that SP9 presents the lowest levelized cost of storage, closely followed by ice. A lower off-peak electricity rate benefits ice more than SP9 or tetradecane because ice has the largest charging cost penalty.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
NASA NTRS1993

Ab initio characterization of ClOOH - Implications for atmospheric chemistry

The equilibrium structure, dipole moment, harmonic vibrational frequencies, and infrared intensities of ClOOH are determined using the CCSD(T) (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) electronic structure method in conjunction with a TZ2P (triple xi plus double polarization) basis set. The heat of formation of CIOOH is determined (using two different isodesmic reactions) to be +1.5 +/- 1 kcal/mol at 0 K or +0.2 +/- 1 kcal/mol at 298.15 K. Using the computed heat of formation, we examined the stability of ClOOH with respect to the ClO + OH, ClOO + H, and HOO + Cl dissociation limits. Since ClOOH is found to be quite stable, it is argued that the chemistry of ClOOH should be included in any accurate modeling of the stratosphere.

Lee, Timothy J.↗
DOE OSTI2023

Triple Excitations in Green’s Function Coupled Cluster Solver for Studies of Strongly Correlated Systems in the Framework of Self-Energy Embedding Theory

Embedding theories became important approaches used for accurate calculations of both molecules and solids. In these theories, a small chosen subset of orbitals is treated with an accurate method, called an impurity solver, capable of describing higher correlation effects. Ideally, such a chosen fragment should contain multiple orbitals responsible for the chemical and physical behavior of the compound. Handling a large number of chosen orbitals presents a very significant challenge for the current generation of solvers used in the physics and chemistry community. Here, we develop a Green’s function coupled cluster singles doubles and triples (GFCCSDT) solver that can be used for a quantitative description in both molecules and solids. This solver allows us to treat orbital spaces that are inaccessible to other accurate solvers. At the same time, GFCCSDT maintains high accuracy of the resulting self-energy. Moreover, in conjunction with the GFCCSD solver, it allows us to test the systematic convergence of computational studies. Developing the CC family of solvers paves the road to fully systematic Green’s function embedding calculations in solids. In this paper, we focus on the investigation of GFCCSDT self-energies for a strongly correlated problem of SrMnO 3 solid. Subsequently, we apply this solver to solid MnO showing that an approximate variant of GFCCSDT is capable of yielding a high accuracy orbital resolved spectral function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electronic effects in radiation-induced collision cascades in nickel

The accurate treatment of electronic effects in multi-million-atom simulations of radiation-induced collision cascades is crucial for reliable predictions of primary radiation damage. In this work, we explore the fidelity of a recently developed two-temperature molecular dynamics model implementing an electron density-dependent coupling of electronic and atomic subsystems for cascade simulations in nickel. We show that the parameter-free model realistically captures the instantaneous energy losses during all stages of the highly nonequilibrium cascade process. Our simulations predict two distinct coupling regimes, corresponding to the rapid energy losses through electronic stopping in the early stages of the cascade and to the slow equilibration through the electron-phonon coupling mechanism in the later stages, without the use of separate models or coupling terms. The intermediate stage of the cascade dynamics displays a complex energy transfer between the subsystems, which cannot be interpreted by comparison to either electronic stopping or electron-phonon coupling theories. We therefore compare the predicted atomic mixing, which is sensitive to the energy losses during the intermediate cascade stage, with experimental ion beam mixing measurements. We find good agreement with the experiments, validating the coupling model for the intermediate stage of the cascade. Predictions of final defect numbers and cluster sizes are found in line with the results from conventional electronic stopping-based methods, while significantly reducing the theoretical uncertainty in the outcomes of conventional models stemming from arbitrary choices of thresholds for different coupling terms. Our results represent a notable improvement in cascade damage predictions in nickel, providing validation of the electron density-dependent coupling model for radiation damage simulations in general. The results lead us to propose an interpretation of the electronic energy losses in the intermediate regime of velocities, where we find an effectively nonlinear dissipation.

Crystal defects↗
DOE OSTI2025

Nuclear Schiff Moments and CP Violation

This article reviews the calculation of nuclear Schiff moments, which one must know in order to interpret experiments that search for time-reversal-violating electric dipole moments in certain atoms and molecules. After briefly reviewing the connection between dipole moments and CP violation in and beyond the Standard Model of particle physics; Schiff's theorem, which concerns the screening of nuclear electric dipole moments by electrons; Schiff moments; and experiments to measure dipole moments in atoms and molecules, this review examines attempts to compute Schiff moments in nuclei such as 199 Hg and octupole-deformed isotopes such as 225 Ra, which are particularly useful in experiments. It then turns to ab initio nuclear-structure theory, describing ways in which both the in-medium similarity renormalization group and coupled-cluster theory can be used to compute important Schiff moments more accurately than the less controlled methods that have been applied so far.

CP violation↗
DOE OSTI2023

A promising intersection of excited‐state‐specific methods from quantum chemistry and quantum Monte Carlo

Abstract We present a discussion of recent progress in excited‐state‐specific quantum chemistry and quantum Monte Carlo alongside a demonstration of how a combination of methods from these two fields can offer reliably accurate excited state predictions across singly excited, doubly excited, and charge transfer states. Both of these fields have seen important advances supporting excited state simulation in recent years, including the introduction of more effective excited‐state‐specific optimization methods, improved handling of complicated wave function forms, and ways of explicitly balancing the quality of wave functions for ground and excited states. To emphasize the promise that exists at this intersection, we provide demonstrations using a combination of excited‐state‐specific complete active space self‐consistent field theory, selected configuration interaction, and state‐specific variance minimization. These demonstrations show that combining excited‐state‐specific quantum chemistry and variational Monte Carlo can be more reliably accurate than either equation of motion coupled cluster theory or multi‐reference perturbation theory, and that it can offer new clarity in cases where existing high‐level methods do not agree. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Quantum Chemistry

Otis, Leon↗