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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Thermofield Theory for Finite-Temperature Electronic Structure

Wave function methods have offered a robust, systematically improvable means to study ground-state properties in quantum many-body systems. Theories like coupled cluster and their derivatives provide highly accurate approximations to the energy landscape at a reasonable computational cost. Analogues of such methods to study thermal properties, though highly desirable, have been lacking because evaluating thermal properties involve a trace over the entire Hilbert space, which is a formidable task. Besides, excited-state theories are generally not as well studied as ground-state ones. In this mini-review, we present an overview of a finite-temperature wave function formalism based on thermofield dynamics to overcome these difficulties. Thermofield dynamics allows us to map the equilibrium thermal density matrix to a pure state, i.e., a single wave function, albeit in an expanded Hilbert space. Ensemble averages become expectation values over this so-called thermal state. Around this thermal state, we have developed a procedure to generalize ground-state wave function theories to finite temperatures. As explicit examples, we highlight formulations of mean-field, configuration interaction, and coupled cluster theories for thermal properties of Fermions in the grand-canonical ensemble. To assess the quality of these approximations, we also show benchmark studies for the one-dimensional Hubbard model, while comparing against exact results. We will see that the thermal methods perform similarly to their ground-state counterparts, while merely adding a prefactor to the asymptotic computational cost. Furthermore, they also inherit all the properties, good or bad, from the ground-state methods, signifying the robustness of our formalism and the scope for future development.

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

Comparison of Computational Strategies for the Calculation of the Electronic Coupling in Intermolecular Energy and Electron Transport Processes

Electronic couplings in intermolecular electron and energy transfer processes calculated by six different existing computational techniques are compared to nonorthogonal configuration interaction for fragments (NOCI-F) results. The paper addresses the calculation of the electronic coupling in diketopyrrolopyrol, tetracene, 5,5'-difluoroindigo, and benzene–Cl for hole and electron transport, as well as the local exciton and singlet fission coupling. NOCI-F provides a rigorous computational scheme to calculate these couplings, but its computational cost is rather elevated. The here-considered ab initio Frenkel–Davydov (AIFD), Dimer projection (DIPRO), transition dipole moment coupling, Michl–Smith, effective Hamiltonian, and Mulliken–Hush approaches are computationally less demanding, and the comparison with the NOCI-F results shows that the NOCI-F results in the couplings for hole and electron transport are rather accurately predicted by the more approximate schemes but that the NOCI-F exciton transfer and singlet fission couplings are more difficult to reproduce.

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

Simulating the Excited-State Dynamics of Polaritons with Ab Initio Multiple Spawning

Over the past decade, there has been a growth of interest in polaritonic chemistry, where the formation of hybrid light–matter states (polaritons) can alter the course of photochemical reactions. These hybrid states are created by strong coupling between molecules and photons in resonant optical cavities and can even occur in the absence of light when the molecule is strongly coupled with the electromagnetic fluctuations of the vacuum field. Here, we present a first-principles model to simulate nonadiabatic dynamics of such polaritonic states inside optical cavities by leveraging graphical processing units (GPUs). Our first implementation of this model is specialized for a single molecule coupled to a single-photon mode confined inside the optical cavity but with any number of excited states computed using complete active space configuration interaction (CASCI) and a Jaynes–Cummings-type Hamiltonian. Using this model, we have simulated the excited-state dynamics of a single salicylideneaniline (SA) molecule strongly coupled to a cavity photon with the ab initio multiple spawning (AIMS) method. We demonstrate how the branching ratios of the photodeactivation pathways for this molecule can be manipulated by coupling to the cavity. We also show how one can stop the photoreaction from happening inside of an optical cavity. Finally, we also investigate cavity-based control of the ordering of two excited states (one optically bright and the other optically dark) inside a cavity for a set of molecules, where the dark and bright states are close in energy.

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

Kohn–Sham Density in a Slater Orbital Basis Set

Finite, atom-centered Slater basis sets are used to determine approximate Kohn–Sham molecular orbitals. This is achieved by minimizing the kinetic energy plus the sum-squared difference between the Kohn–Sham density and the full configuration interaction density. As a result of the finite basis, a weight factor is introduced to balance the two minimization components. Results herein show that this can be done systematically, without sensitive dependence on the choice of scaling factor. In addition, the algorithm is applied to the LiH diatomic for fractional electron counts, where stretching the bond introduces significant reorganization of the electron density. As a result, the analysis will show the correct KS orbital structure and reveal the effects of correlation and electron locality on the KS solutions.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

COLUMBUS─An Efficient and General Program Package for Ground and Excited State Computations Including Spin–Orbit Couplings and Dynamics

The COLUMBUS program system provides the tools for performing high-level multireference (MR) computations, including the multireference configuration interaction (MRCI) method and its multireference averaged quadratic coupled cluster (MR-AQCC) extension, allowing computations on a wide range of fascinating atomic and molecular systems, including the treatment of open-shells and complicated excited state phenomena. The inclusion of spin−orbit coupling (SOC) directly within the MRCI step enables the description of systems containing heavy elements, such as lanthanides and actinides, whose properties are strongly influenced by SOC. Analytic energy gradients and nonadiabatic couplings at the correlated MRCI level provide the foundation for a variety of dynamics studies, giving insight into ultrafast photochemistry. New and ongoing method developments in COLUMBUS include the computation of spin densities, improved descriptions of ionic states, enhancements to the AQCC method, and the porting of COLUMBUS to graphical processing units (GPUs). New external interfaces enable an enhanced description of electronic resonances and molecules in strong laser fields. This work highlights these new developments while providing a detailed account of the diverse applications of COLUMBUS in recent years.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Analysis of Fourth-, Fifth-, and Infinite-Order Triple Excitations in Unitary Coupled Cluster Theory

Here, in this work, we introduce a perturbative correction to the unitary coupled cluster method with single and double excitations (UCCSD) that incorporates the effects of missing triple excitations through fifth-order in many-body perturbation theory (MBPT). Referred to as UCCSD[T-5], this method is benchmarked alongside the previously developed UCCSD[T] to lend insight into the behavior of perturbative triples corrections relative to UCCSDT, which inherently provides an infinite-order treatment of triple excitations, as well as full configuration interaction (FCI). Two key findings emerge from this analysis. First, UCCSD[T] consistently yields ground-state energies in closest agreement with FCI, outperforming both UCCSD[T-5] and UCCSDT. Second, UCCSD[T-5] largely emulates the behavior of UCCSDT, suggesting a close relationship between fifth- and infinite-order triple-excitation contributions. Given the growing interest in UCC ansätze for quantum computing and the limitations of current quantum hardware, these results highlight the potential of classically computed perturbative corrections within UCC theory to capture triple-excitation effects without the additional quantum resources required by the UCCSDT ansatz.

Windom, Zachary W. [Oak Ridge National Laboratory ↗
DOE OSTI2025

The Singlet–Triplet Gap of Cyclobutadiene: The CIPSI-Driven CC( P ; Q ) Study

An accurate determination of singlet−triplet gaps in biradicals, including cyclobutadiene in the automerization barrier region where one has to balance the substantial nondynamical many-electron correlation effects characterizing the singlet ground state with the predominantly dynamical correlations of the lowest-energy triplet, remains a challenge for many quantum chemistry methods. High-level coupled-cluster (CC) approaches, such as the CC method with a full treatment of singly, doubly, and triply excited clusters (CCSDT), are often capable of providing reliable results, but routine application of such methods is hindered by their high computational costs. We have recently proposed a practical alternative to converging the CCSDT energetics at small fractions of the computational effort, even when electron correlations become stronger and connected triply excited clusters are larger and nonperturbative, by merging the CC(P;Q) moment expansions with the selected configuration interaction methodology abbreviated as CIPSI. We demonstrate that one can accurately approximate the highly accurate CCSDT potential surfaces characterizing the lowest singlet and triplet states of cyclobutadiene along the automerization coordinate and the gap between them using tiny fractions of triply excited cluster amplitudes identified with the help of relatively inexpensive CIPSI Hamiltonian diagonalizations.

Basis sets↗
DOE OSTI2026

Bond Dissociation Energies of the Actinide Halides AnX, An = Ac–Lr and X = F–I, Utilizing Relativistic Composite Coupled Cluster Approaches

Bond dissociation energies (BDEs) have been calculated for the set of actinide halides AnX with An=Ac, Pa, and Np-Lr and X=F-I. Two composite thermochemistry methods based on the Feller-Peterson-Dixon (FPD) approach have been utilized, one involving spinor-based relativistic CCSD(T) calculations where spin-orbit (SO) was included at the orbital level and another using scalar relativistic CCSD(T) with a posteriori SO contributions based on 2-component multireference configuration interaction calculations. The method that was chosen for a given actinide halide was based on which representation yielded the best single determinant reference determinant for the coupled cluster calculation. The spinor-based method was chosen for all cases except for AmX, CmX, and BkX. Both composite approaches included contributions accounting for basis set truncation, outer-core correlation, the Gaunt interaction, and QED. The scalar FPD results, as well as the spinor-based calculations for AcF, also included higher order electron correlation up through CCSDT(Q). In addition to BDEs, CCSD(T) equilibrium bond lengths, harmonic frequencies, and vibrational anharmonicity constants are reported for all species. Last, the FPD BDEs for the fluorides were used to confirm the trend across the actinide series previously predicted by Gibson using bonding models based atomic promotion energies that provide a single 6d electron for bonding. In particular the local minimum in the BDEs at AmF is confirmed in the present calculations. Furthermore, the BDEs for LrX are predicted to be slightly larger than those of AcX, making them the largest in the actinide halide series.

Actinides↗
DOE OSTI2020

The Ground State Electronic Energy of Benzene

We report here on the findings of a blind challenge devoted to determining the frozen-core, full configuration interaction (FCI) ground-state energy of the benzene molecule in a standard correlation-consistent basis set of double-ζ quality. As a broad international endeavor, our suite of wave function-based correlation methods collectively represents a diverse view of the high-accuracy repertoire offered by modern electronic structure theory. In our assessment, the evaluated high-level methods are all found to qualitatively agree on a final correlation energy, with most methods yielding an estimate of the FCI value around -863 mE H . However, we find the root-mean-square deviation of the energies from the studied methods to be considerable (1.3 mE H ), which in light of the acclaimed performance of each of the methods for smaller molecular systems clearly displays the challenges faced in extending reliable, near-exact correlation methods to larger systems. While the discrepancies exposed by our study thus emphasize the fact that the current state-of-the-art approaches leave room for improvement, we still expect the present assessment to provide a valuable community resource for benchmark and calibration purposes going forward.

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

A Comparison of Exact and Model Exchange–Correlation Potentials for Molecules

Accurate exchange–correlation (XC) potentials for three-dimensional systems–via solution of the inverse density functional theory (DFT) problem–are now available to test the quality of DFT approximations. Herein, the exact XC potential for seven molecules–dihydrogen at four different bond-lengths, lithium hydride, water, and ortho-benzyne–are computed from full configuration interaction reference densities. These are compared to model XC potentials from nonlocal (B3LYP, HSE06, SCAN0, and M08-HX) and semilocal/local (SCAN, PBE, and PW92) XC functionals. Whereas for most systems, relative errors in the ground-state densities are O(10 –3 –10 –2 ) , the model XC potentials have much higher errors of O(10 –1 –10 0 ) . Among the model XC functionals, SCAN0 offers the best agreement with the exact XC potential, underlining the significance of satisfying exact conditions as well as including nonlocal effects in XC functionals. This work indicates that tests against the exact XC potential will provide a promising new direction for building more accurate XC functionals for DFT.

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

Data-Driven Refinement of Electronic Energies from Two-Electron Reduced-Density-Matrix Theory

The exponential computational cost of describing strongly correlated electrons can be mitigated by adopting a reduced-density-matrix (RDM)-based description of the electronic structure. While variational two-electron RDM (v2RDM) methods can enable large-scale calculations on such systems, the quality of the solution is limited by the fact that only a subset of known necessary N-representability constraints can be applied to the 2RDM in practical calculations. Here, we demonstrate that violations of partial three-particle (T1 and T2) N-representability conditions, which can be evaluated with knowledge of only the 2RDM, can serve as physics-based features in a machine-learning (ML) protocol for improving energies from v2RDM calculations that consider only two-particle (PQG) conditions. Proof-of-principle calculations demonstrate that the model yields substantially improved energies, relative to reference values from configuration-interaction-based calculations.

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

Exact and Model Exchange-Correlation Potentials for Open-Shell Systems

The conventional approaches to the inverse density functional theory problem typically assume nondegeneracy of the Kohn–Sham (KS) eigenvalues, greatly hindering their use in open-shell systems. Here, we present a generalization of the inverse density functional theory problem that can seamlessly admit degenerate KS eigenvalues. Additionally, we allow for fractional occupancy of the Kohn–Sham orbitals to also handle noninteracting ensemble-v-representable densities, as opposed to just noninteracting pure-v-representable densities. We present the exact exchange-correlation (XC) potentials for six open-shell systems–four atoms (Li, C, N, and O) and two molecules (CN and CH 2 )–using accurate ground-state densities from configuration interaction calculations. We compare these exact XC potentials with model XC potentials obtained using nonlocal (B3LYP, SCAN0) and local/semilocal (SCAN, PBE, PW92) XC functionals. Although the relative errors in the densities obtained from these DFT functionals are of $O$(10 –3 to 10 –2 ), the relative errors in the model XC potentials remain substantially large–$O$(10 –1 to 10 0 ).

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

Exploiting a Shortcoming of Coupled-Cluster Theory: The Extent of Non-Hermiticity as a Diagnostic Indicator of Computational Accuracy

The fundamental non-Hermitian nature of the forms of the coupled-cluster (CC) theory widely used in quantum chemistry has usually been viewed as a negative, but the present paper shows how this can be used to an advantage. Specifically, the non-symmetric nature of the reduced one-particle density matrix (in the molecular orbital basis) is advocated as a diagnostic indicator of computational quality. In the limit of the full coupled-cluster theory [which is equivalent to full configuration interaction (FCI)], the electronic wave function and correlation energy are exact within a given one-particle basis set, and the symmetric character of the exact density matrix is recovered. The extent of the density matrix asymmetry is shown to provide a measure of “how difficult the problem is” (like the well-known T 1 diagnostic), but its variation with the level of theory also gives information about “how well this particular method works”, irrespective of the difficulty of the problem at hand. The proposed diagnostic is described and applied to a select group of small molecules, and an example of its overall utility for the practicing quantum chemist is illustrated through its application to the beryllium dimer (Be 2 ). Future application of this idea to excited states, open-shell systems, and symmetry-breaking problems and an extension of the method to the two-particle density are then proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

High-Performance Semiempirical Excited-State Molecular Dynamics Powered by Graphics Processing Units

Here, this Letter introduces excited-state molecular dynamics in PYSEQM, a GPU-accelerated semiempirical quantum chemistry engine implemented in PyTorch. The new module enables Born–Oppenheimer molecular dynamics (BOMD) using configuration-interaction singles and random phase approximation for excited states, allowing long trajectories and large statistical ensembles to be simulated efficiently on a single GPU. We also implement an extended Lagrangian excited-state BOMD (XL-ESMD) scheme that propagates auxiliary electronic variables, enabling relaxed ground and excited-state convergence thresholds without compromising energy conservation. The excited-state BOMD implementation scales smoothly from small chromophores to a nearly 900-atom dendrimer (taking 6.5 s per MD step). PYSEQM also supports batched execution, allowing many geometries or trajectories to be evaluated in a single GPU launch, substantially increasing throughput and making ensemble-based protocols routine. As a demonstration, we compute absorption, emission, and infrared spectra from trajectories propagated on the ground and first excited states. The XL-ESMD scheme yields identical spectra at significantly lower computational cost, establishing the role of extended Lagrangian based dynamics for efficient excited-state BOMD simulations. Beyond raw performance, PYSEQM’s PyTorch foundation provides automatic differentiation for forces, efficient GPU batching, and seamless interfacing with machine learning models. These capabilities position PYSEQM as a practical platform for machine learning-augmented excited-state dynamics and lay the foundation for future data-driven nonadiabatic excited-state dynamics modeling of ultrafast spectroscopic probes.

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

Transition-Metal-Related Quantum Emitters in Wurtzite AlN and GaN

Transition-metal centers exhibit a paramagnetic ground state in wide-bandgap semiconductors and are promising for nanophotonics and quantum information processing. Specifically, there is a growing interest in discovering prominent paramagnetic spin defects that can be manipulated using optical methods. Here, we investigate the electronic structure and magneto-optical properties of Cr and Mn substitutional centers in wurtzite AlN and GaN. We use state-of-the-art hybrid density functional theory calculations to determine level structure, stability, optical signatures, and magnetic properties of these centers. The excitation energies are calculated using the constrained occupation approach and rigorously verified with the complete active space configuration interaction approach. Our simulations of the photoluminescence spectra indicate that $Cr$$^{1+}_{Al}$ in AlN and $Cr$$^{1+}_{Ga}$ in GaN are responsible for the observed narrow quantum emission near 1.2 eV. We compute the zero-field splitting (ZFS) parameters and outline an optical spin polarization protocol for $Cr$$^{1+}_{Al}$ and $Cr$$^{1+}_{Ga}$. Our results demonstrate that these centers are promising candidates for spin qubits.

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

Satellite-Dominated Sulfur L 2,3 X-ray Emission of Alkaline Earth Metal Sulfides

The sulfur L 2,3 X-ray emission spectra of the alkaline earth metal sulfides BeS, MgS, CaS, SrS, and BaS are investigated and compared with spectra calculations based on density functional theory. Very distinct spectral shapes are found for the different compounds. With decreasing electronegativity of the cation, that is, increasing ionic bonding character, the upper valence band width and its relative spectral intensity decrease. These general trends are qualitatively reproduced by the spectra calculations, which give quite an accurate description of the spectral shapes in the upper valence band region. On the low energy side of the sulfur 3s → 2p transition dominating the spectra, we find strong satellites caused by "semi-Auger" decays involving configuration interaction. These satellites, previously believed to be energetically forbidden for sulfur L 2,3 emission and only observed for the L 2,3 emission of Cl to Cr, increase in intensity as the bonding character becomes more ionic and dominate the spectra for SrS and BaS. The intensities, energies, and widths of the satellites vary strongly between the investigated compounds, giving a very specific spectral fingerprint that can be used for speciation analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Understanding the Competition between Alcohol Formation and Dimerization during Electrochemical Reduction of Aromatic Carbonyl Compounds

The electrochemical reductive dimerization of small aromatic carbonyl compounds derived from lignocellulosic biomass is a crucial C−C coupling reaction for upgrading small molecules to longchain hydrocarbons, particularly in the synthesis of drop-in sustainable aviation fuels. Although other electrochemical reduction reactions of these reactants (i.e., hydrogenation and hydrogenolysis) have undergone extensive mechanistic investigation, the understanding of dimerization remains relatively underdeveloped. Most importantly, there is a lack of understanding of the selectivity-determining step between dimerization and monomer reduction and critical factors that can affect this step. In this study, we provide a comprehensive mechanistic model to explain the competition between dimerization and monomer reduction of benzaldehyde under various conditions. Our model proposes that the selectivity between dimerization and monomer reduction depends on the competition between desorption of a ketyl radical from the electrode, necessary for dimerization, and further reduction of the ketyl radical to an alcohol on the electrode by proton-coupled electron transfer (PCET). Computationally comparing the adsorption/desorption energy and PCET activation barrier energy is challenging because conventional DFT calculations substantially underestimate the PCET kinetic barriers. In this study, we employed constrained DFTbased configuration interaction (CDFT-CI) to obtain a reliable comparison of these energies. Our mechanistic model was tested and supported by experimental results obtained with four electrodes (Cu, Pb, Bi, graphite), three pH conditions (acidic, neutral, basic), and three potentials. Our study offers a coherent mechanistic foundation that can explain how each of these conditions impacts the desorption and PCET processes and the selectivities for dimerization and alcohol production.

09 BIOMASS FUELS↗
DOE OSTI2024

Unveiling Hidden Shake-Up Features in the Uranyl M 4 -Edge Spectrum

The M 4,5 -edge high energy resolution X-ray absorption near-edge structure (HR-XANES) spectra of actinyls offer valuable insights into the electronic structure and bonding properties of heavy-element complexes. To conduct a comprehensive spectral analysis, it is essential to employ computational methods that accurately account for relativistic effects and electron correlation. In this work, we utilize variational relativistic multireference configurational interaction methods to compute and analyze the X-ray M 4 -edge absorption spectrum of uranyl. By employing these advanced computational techniques, we achieve excellent agreement between the calculated spectral features and experimental observations. Moreover, the calculations unveil significant shake-up features, which arise from the intricate interplay between strongly correlated 3d core-electron and ligand excitations. This research provides important theoretical insights into the spectral characteristics of heavy-element complexes. Furthermore, it establishes the foundation for utilizing M 4,5 -edge spectroscopy as a means to investigate the chemical activities of such complexes. By leveraging this technique, we can gain a deeper understanding of the bonding behavior and reactivity of heavy-element compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗