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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Symmetry-projected cluster mean-field theory applied to spin systems

We introduce S z spin-projection based on cluster mean-field theory and apply it to the ground state of strongly correlated spin systems. In cluster mean-fields, the ground state wavefunction is written as a factorized tensor product of optimized cluster states. In previous work, we have focused on unrestricted cluster mean-field, where each cluster is S z symmetry adapted. We here remove this restriction by introducing a generalized cluster mean-field (GcMF) theory, where each cluster is allowed to access all S z sectors, breaking S z symmetry. In addition, a projection scheme is used to restore global S z , which gives rise to the S z spin-projected generalized cluster mean-field (S z GcMF). Both of these extensions contribute to accounting for inter-cluster correlations. We benchmark these methods on the 1D, quasi-2D, and 2D J 1 – J 2 and XXZ Heisenberg models. Furthermore, our results indicate that the new methods (GcMF and S z GcMF) provide a qualitative and semi-quantitative description of the Heisenberg lattices in the regimes considered, suggesting them as useful references for further inter-cluster correlations, which are discussed in this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

High-level coupled-cluster energetics by merging moment expansions with selected configuration interaction

Inspired by our earlier semi-stochastic work aimed at converging high-level coupled-cluster (CC) energetics, we propose a novel form of the CC(P; Q) theory in which the stochastic Quantum Monte Carlo propagations, used to identify dominant higher-than-doubly excited determinants, are replaced by the selected configuration interaction (CI) approach using the perturbative selection made iteratively (CIPSI) algorithm. The advantages of the resulting CIPSI-driven CC(P; Q) methodology are illustrated by a few molecular examples, including the dissociation of F 2 and the automerization of cyclobutadiene, where we recover the electronic energies corresponding to the CC calculations with a full treatment of singles, doubles, and triples based on the information extracted from compact CI wave functions originating from relatively inexpensive Hamiltonian diagonalizations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electronic structure theory on modeling short-range noncovalent interactions between amino acids

While short-range noncovalent interactions (NCIs) are proving to be of importance in many chemical and biological systems, these atypical bindings happen within the so-called van der Waals envelope and pose an enormous challenge for current computational methods. We introduce SNCIAA, a database of 723 benchmark interaction energies of short-range noncovalent interactions between neutral/charged amino acids originated from protein x-ray crystal structures at the “gold standard” coupled-cluster with singles, doubles, and perturbative triples/complete basis set [CCSD(T)/CBS] level of theory with a mean absolute binding uncertainty less than 0.1 kcal/mol. Subsequently, a systematic assessment of commonly used computational methods, such as the second-order Møller−Plesset theory (MP2), density functional theory (DFT), symmetry-adapted perturbation theory (SAPT), composite electronic-structure methods, semiempirical approaches, and the physical-based potentials with machine learning (IPML) on SNCIAA is carried out. It is shown that the inclusion of dispersion corrections is essential even though these dimers are dominated by electrostatics, such as hydrogen bondings and salt bridges. Overall, MP2, ωB97M-V, and B3LYP+D4 turned out to be the most reliable methods for the description of short-range NCIs even in strongly attractive/repulsive complexes. SAPT is also recommended in describing short-range NCIs only if the δMP2 correction has been included. The good performance of IPML for dimers at close-equilibrium and long-range conditions is not transferable to the short-range. We expect that SNCIAA will assist the development/improvement/validation of computational methods, such as DFT, force-fields, and ML models, in describing NCIs across entire potential energy surfaces (short-, intermediate-, and long-range NCIs) on the same footing.

Chemistry↗
NASA NTRS1994

Symmetry breaking in O4(+): An application of the Brueckner coupled-cluster method

A recent calculation of the antisymmetric stretch frequency for the rectangular structure of quartet O4(+) using the singles and doubles quadratic configuration interaction method with a perturbational estimate of connected triple excitations (QCISD(T)) method gave a value of 3710 cm(exp -1). This anomalous frequency is shown to be a consequence of symmetry breaking effects, which occur even though the QCISD(T) solution derived from a delocalized SCF reference function lies energetically well below the two localized (symmetry-broken) solutions at the equilibrium geometry. The symmetry breaking is almost eliminated at the CCSD level of theory, but the small remaining symmetry breaking effects are magnified at the CCSD(T) level of theory so that the antisymmetric stretch frequency is still significantly in error. The use of the Brueckner coupled cluster method, however, leads to a symmetrical solution which is free of symmetry breaking effects, with an antisymmetric stretch frequency of 1322 cm(exp -1), in good agreement with our earlier calculations using the complete active space self consistent field/complete active space state interaction (CASSCF/CASSI) method.

Barnes, Leslie A.↗
DOE OSTI2021

NENCI-2021. I. A large benchmark database of non-equilibrium non-covalent interactions emphasizing close intermolecular contacts

In this work, we present NENCI-2021, a benchmark database of ~8000 Non-Equilibirum Non-Covalent Interaction energies for a large and diverse selection of intermolecular complexes of biological and chemical relevance. To meet the growing demand for large and high-quality quantum mechanical data in the chemical sciences, NENCI-2021 starts with the 101 molecular dimers in the widely used S66 and S101 databases and extends the scope of these works by (i) including 40 cation–π and anion–π complexes, a fundamentally important class of non-covalent interactions that are found throughout nature and pose a substantial challenge to theory, and (ii) systematically sampling all 141 intermolecular potential energy surfaces (PESs) by simultaneously varying the intermolecular distance and intermolecular angle in each dimer. Designed with an emphasis on close contacts, the complexes in NENCI-2021 were generated by sampling seven intermolecular distances along each PES (ranging from 0.7× to 1.1× the equilibrium separation) and nine intermolecular angles per distance (five for each ion–π complex), yielding an extensive database of 7763 benchmark intermolecular interaction energies (E int ) obtained at the coupled-cluster with singles, doubles, and perturbative triples/complete basis set [CCSD(T)/CBS] level of theory. The E int values in NENCI-2021 span a total of 225.3 kcal/mol, ranging from -38.5 to +186.8 kcal/mol, with a mean (median) E int value of -1.06 kcal/mol (-2.39 kcal/mol). In addition, a wide range of intermolecular atom-pair distances are also present in NENCI-2021, where close intermolecular contacts involving atoms that are located within the so-called van der Waals envelope are prevalent—these interactions, in particular, pose an enormous challenge for molecular modeling and are observed in many important chemical and biological systems. A detailed symmetry-adapted perturbation theory (SAPT)- based energy decomposition analysis also confirms the diverse and comprehensive nature of the intermolecular binding motifs present in NENCI-2021, which now includes a significant number of primarily induction-bound dimers (e.g., cation–π complexes). NENCI-2021 thus spans all regions of the SAPT ternary diagram, thereby warranting a new four-category classification scheme that includes complexes primarily bound by electrostatics (3499), induction (700), dispersion (1372), or mixtures thereof (2192). A critical error analysis performed on a representative set of intermolecular complexes in NENCI-2021 demonstrates that the E int values provided herein have an average error of ±0.1 kcal/mol, even for complexes with strongly repulsive E int values, and maximum errors of ±0.2–0.3 kcal/mol (i.e., ~±1.0 kJ/mol) for the most challenging cases. For these reasons, we expect that NENCI-2021 will play an important role in the testing, training, and development of next-generation classical and polarizable force fields, density functional theory approximations, wavefunction theory methods, and machine learning based intra- and inter-molecular potentials.

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

A Generalized Variational Principle with Applications to Excited State Mean Field Theory

We present a generalization of the variational principle that is compatible with any Hamiltonian eigenstate that can be specified uniquely by a list of properties. This variational principle appears to be compatible with a wide range of electronic structure methods, including mean field theory, density functional theory, multireference theory, and quantum Monte Carlo. Like the standard variational principle, this generalized variational principle amounts to the optimization of a nonlinear function that, in the limit of an arbitrarily flexible wave function, has the desired Hamiltonian eigenstate as its global minimum. Unlike the standard variational principle, it can target excited states and select individual states in cases of degeneracy or near-degeneracy. As an initial demonstration of how this approach can be useful in practice, we employ it to improve the optimization efficiency of excited state mean field theory by an order of magnitude. With this improved optimization, we are able to demonstrate that the accuracy of the corresponding second-order perturbation theory rivals that of singles-and-doubles equation-of-motion coupled cluster in a substantially broader set of molecules than could be explored by our previous optimization methodology.

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

Unconventional Error Cancellation Explains the Success of Hartree–Fock Density Functional Theory for Barrier Heights

Energy barriers, which control the rates of chemical reactions, are seriously underestimated by computationally efficient semilocal approximations for the exchange-correlation energy. The accuracy of a semilocal density functional approximation is strongly boosted for reaction barrier heights by evaluating that approximation non-self-consistently on Hartree–Fock electron densities, which has been known for ~30 years. Here, the conventional explanation is that the Hartree–Fock theory yields the more accurate density. This work presents a benchmark Kohn–Sham inversion of accurate coupled-cluster densities for the reaction H 2 + F → HHF → H + HF and finds a strong, understandable cancellation between positive (excessively overcorrected) density-driven and large negative functional-driven errors (expected from stretched radical bonds in the transition state) within this Hartree–Fock density functional theory. This confirms earlier conclusions (Kaplan, A. D., et al. J. Chem. Theory Comput. 2023, 19, 532–543) based on 76 barrier heights and three less reliable, but less expensive, fully nonlocal density functional proxies for the exact density.

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

Quantum many-body linear algebra, Hamiltonian moments, and a coupled-cluster inspired framework

Here, we propose a general strategy to develop quantum many-body approximations of primitives in linear algebra algorithms. As a practical example, we introduce a coupled-cluster inspired framework to produce approximate Hamiltonian moments and demonstrate its application in various linear algebra algorithms for ground state estimation. Through numerical examples, we illustrate the difference between the ground-state energies arising from quantum many-body linear algebra and those from the analogous many-body perturbation theory. Our results support the general idea of designing quantum many-body approximations outside of perturbation theory, providing a route to new algorithms and approximations.

Algorithms and data structure↗
DOE OSTI2025

Electron correlation and relativistic effects in the excited states of radium monofluoride

Highly accurate and precise electronic structure calculations of heavy radioactive atoms and their molecules are important for several research areas, including chemical, nuclear, and particle physics. Ab initio quantum chemistry can elucidate structural details in these systems that emerge from the interplay of relativistic and electron correlation effects, but the large number of electrons complicates the calculations, and the scarcity of experiments prevents insightful theory-experiment comparisons. Here we report the spectroscopy of the 14 lowest excited electronic states in the radioactive molecule radium monofluoride (RaF), which is proposed as a sensitive probe for searches of new physics. The observed excitation energies are compared with state-of-the-art relativistic Fock-space coupled cluster calculations, which achieve an agreement of ≥99.64% (within ~12 meV) with experiment for all states. Guided by theory, a firm assignment of the angular momentum and term symbol is made for 10 states and a tentative assignment for 4 states. The role of high-order electron correlation and quantum electrodynamics effects in the excitation energies is studied and found to be important for all states.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

A comparison of QTP functionals against coupled-cluster methods for EAs of small organic molecules

EA-EOM-CCSD electron affinities and LUMO energies of various Kohn–Sham density functional theory (DFT) methods are calculated for an a priori IP benchmark set of 64 small, closed-shell molecules. The purpose of these calculations was to investigate whether the QTP KS-DFT functionals can emulate EA-EOM-CC with only a mean-field approximation. We show that the accuracy of DFT—relative to CCSD—improves significantly when elements of correlated orbital theory are introduced into the parameterization to define the QTP family of functionals. In particular, QTP(02), which has only a single range separation parameter, provides results accurate to a MAD of <0.15 eV for the whole set of 64 molecules compared to EA-EOM-CCSD, far exceeding the results from the non-QTP family of density functionals.

Chemistry↗
DOE OSTI2025

Impact of solvation on the electronic resonances in uracil

Interactions of low-energy electrons with the DNA and RNA nucleobases are known to form metastable states, known as electronic resonances. In this work, we study electron attachment to solvated uracil, an RNA nucleobase, using the orbital stabilization method at the Equation of Motion-Coupled Cluster for Electron Affinities with Singles and Doubles (EOM-EA-CCSD) level of theory with the Effective Fragment Potential (EFP) solvation method. We benchmarked the approach using multireference methods, as well as by comparing EFP and full quantum calculations. The impact of solvation on the first one particle (1p) shape resonance, formed by electron attachment to the π* LUMO orbital, as well as the first two particle one hole (2p1h) resonance, formed by electron attachment to neutral uracil's π–π* excited state, was investigated. We used molecular dynamics simulations for solvent configurations and applied charge stabilization technique-based biased sampling to procure configurations adequate to cover the entire range of the electron attachment energy distribution. The electron attachment energy in solution is found to be distributed over a wide range of energies, between 4.6 eV to 6.8 eV for the 2p1h resonance, and between −0.1 eV to 2 eV for the 1p resonance. The solvent effects were similar for the two resonances, indicating that the exact electron density of the state is not as important as the solvent configurations. Multireference calculations extended the findings showing that solvation effects are similar for the lowest four resonances, further indicating that the specific solute electron density is not as important, but rather the water configurations play the most important role in solvation effects. Lastly, by comparing bulk solvation to clusters of uracil with a few water molecules around it, we find that the impact of microsolvation is very different from that of bulk solvation.

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

A spatially-resolved model of neutron-irradiated tungsten coupling stochastic cluster dynamics and finite deformation plasticity

Structural materials used in nuclear reactors face severe degradation in mechanical properties, such as hardening and embrittlement. At the microscopic scale, this occurs due to creation and accumulation of irradiation-induced defects and their interaction with system dislocations. Although techniques exist which can model evolution of irradiation defects, for instance kinetic transport theory-based models, their interaction with mechanical deformation of the bulk material has not been investigated extensively. In this work, we demonstrate a novel spatially-resolved multiscale coupling between microscopic irradiation defect evolution, modeled using Stochastic Cluster Dynamics (SCD) and macroscopic mechanical deformation modeled using a finite-deformation plasticity model. SCD is used to determine the statistically averaged defect cluster spacing, dependent on operating conditions such as irradiation dose and temperature. This acts as an initial condition that governs the critical resolved shear stress of dislocation glide in the macroscopic plasticity model. This framework is used to predict mechanical behavior in post-mortem test of irradiated Tungsten samples, which has found its importance as structural material used in nuclear reactors. The results obtained using the coupled approach are in good agreement with experimental data of uniaxial tension tests. The model is able to capture the effect of temperature and irradiation dose on the material hardening. Two methods are proposed to estimate hardness – using Tabor's Law relating uniaxial yield stress to hardness and from flat-punch simulations. The results are in reasonable agreement with hardness data from micro-indentation experiments of irradiated Tungsten samples. Finally, the model is also able to reveal microstructural details such as spatial variation in defect density and local stress.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

Simulated field-modulated x-ray absorption in titania

Here, we present a method to compute the x-ray absorption near-edge structure (XANES) spectra of solid-state transition metal oxides using real-time time-dependent density functional theory, including spin–orbit coupling effects. This was performed on bulk-mimicking anatase titania (TiO 2 ) clusters, which allows for the use of hybrid functionals and atom-centered all electron basis sets. Furthermore, this method was employed to calculate the shifts in the XANES spectra of the Ti L-edge in the presence of applied electric fields to understand how external fields can modify the electronic structure, and how this can be probed using x-ray absorption spectroscopy. Specifically, the onset of t 2g peaks in the Ti L-edge was observed to red shift and the e g peaks were observed to blue shift with increasing fields, attributed to changes in the hybridization of the conduction band (3d) orbitals.

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

Extending GPU-accelerated Gaussian integrals in the TeraChem software package to f type orbitals: Implementation and applications

Here, the increasing availability of graphics processing units (GPUs) for scientific computing has prompted interest in accelerating quantum chemical calculations through their use. However, the complexity of integral kernels for high angular momentum basis functions often limits the utility of GPU implementations with large basis sets or for metal containing systems. In this work, we report the implementation of f function support in the GPU-accelerated TeraChem software package through the development of efficient kernels for the evaluation of Hamiltonian integrals. The high efficiency of the resulting code is demonstrated through density functional theory (DFT) calculations on increasingly large organic molecules and transition metal complexes, as well as coupled cluster singles and doubles calculations on water clusters. Preliminary investigations into Ni(I) catalysis with DFT and the photochemistry of MnH(CH 3 ) with complete active space self-consistent field are also carried out. Overall, our GPU-accelerated software appears to be well-suited for fast simulation of large transition metal containing systems, as well as organic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

The calculation of the vibrational frequencies of CuCO+, NiCO and CuCH3

The vibrational frequencies of CuCO+, NiCO, and CuCH3 are computed at both the self-consistent-field (SCF) and coupled-cluster singles and doubles, with a perturbational estimate of the triples (CCSD(T)), levels of theory. Overall the SCF frequencies are in qualitative agreement with the CCSD(T) results. The calculations show that the frequencies for the electrostatically bound CuCO+ are quite different from the datively bound NiCO. The CCSD(T) calculations support a previous suggestion that the C-H stretches in CuCH3 have been misassigned.

Sodupe, M.↗
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↗
NASA NTRS2015

Analysis of Fiber Clustering in Composite Materials Using High-Fidelity Multiscale Micromechanics

A new multiscale micromechanical approach is developed for the prediction of the behavior of fiber reinforced composites in presence of fiber clustering. The developed method is based on a coupled two-scale implementation of the High-Fidelity Generalized Method of Cells theory, wherein both the local and global scales are represented using this micromechanical method. Concentration tensors and effective constitutive equations are established on both scales and linked to establish the required coupling, thus providing the local fields throughout the composite as well as the global properties and effective nonlinear response. Two nondimensional parameters, in conjunction with actual composite micrographs, are used to characterize the clustering of fibers in the composite. Based on the predicted local fields, initial yield and damage envelopes are generated for various clustering parameters for a polymer matrix composite with both carbon and glass fibers. Nonlinear epoxy matrix behavior is also considered, with results in the form of effective nonlinear response curves, with varying fiber clustering and for two sets of nonlinear matrix parameters.

composite materials↗
DOE OSTI2025

Repartitioning the Hamiltonian in many-body second-order Brillouin–Wigner perturbation theory: Uncovering new size-consistent models

Second-order Møller-Plesset perturbation theory is well-known as a computationally inexpensive approach to the electron correlation problem that is size-consistent with a size-consistent reference but fails to be regular. On the other hand, the less well-known many-body version of Brillouin-Wigner perturbation theory has the reverse properties: it is regular but fails to be size-consistent when used with the standard MP partitioning. Consequently, its widespread use remains limited. In this work, we analyze the ways in which it is possible to use alternative non-MP partitions of the Hamiltonian to yield variants of BW2 that are size-consistent as well as regular. We show that there is a vast space of such BW2 theories and also show that it is possible to define a repartitioned BW2 theory from the ground state density alone, which regenerates the exact correlation energy. We also provide a general recipe for deriving regular, size-consistent, and size-extensive partitions from physically meaningful components, and we apply the result to small model systems. The scope of these results appears to further set the stage for a revival of BW2 in quantum chemistry.

Ab initio perturbation↗