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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
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

Electron-impact ionization from excited states method

We present a distorted-wave with exchange (DWE) formulation for computing electron-impact ionization (EII) cross sections within the recently developed excited states method (ESM) for plasmas. The ESM provides a self-consistent quantum-mechanical description of both bound and continuum electronic states in dense plasmas, incorporating finite-temperature and screening effects absent in isolated-atom approaches. Using this framework, we calculate EII cross sections for lithium across a wide range of temperatures and densities. We show that the ESM reproduces the isolated-atom limit at low densities while capturing strong plasma effects, such as pressure ionization and shape resonances, at solid density. Comparisons with isolated-atom DWE and average-atom (AA) calculations reveal that, although AA cross sections can approximate configuration average behavior, the ESM provides more accurate, state-resolved answers. In conclusion, these results demonstrate that the ESM allows one to obtain rate coefficients for collisional-radiative modeling of plasmas out of local thermodynamical equilibrium.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Excited-state uncertainties in lattice-QCD calculations of multi-hadron systems

Excited-state effects lead to hard-to-quantify systematic uncertainties in lattice quantum chromodynamics (LQCD) spectroscopy calculations when computationally accessible imaginary times are smaller than inverse excitation gaps, as often arises for multi-hadron systems with signal-to-noise problems. Lanczos residual bounds address this by providing two-sided constraints on energies that do not require assumptions beyond Hermiticity, but often give very conservative systematic uncertainty estimates. Here, a more-constraining set of gap bounds is introduced for hadron spectroscopy. These bounds provide tighter constraints whose validity requires an explicit assumption about an energy gap. Exactly solvable lattice field theory correlators are used to test the utility of residual and gap bounds at finite and infinite statistics. Two-sided bounds and other analysis methods are then applied to a high-statistics LQCD calculation of nucleon-nucleon scattering at $m_π\sim 800$ MeV. Generalized eigenvalue problem (GEVP) and Lanczos energy estimators are compatible when applied to the same correlator data, but analyses including different interpolating operators show statistically significant inconsistencies. However, two-sided bounds from all operators are consistent. Under the assumption that the number of energy levels below $NΔ$ and $ΔΔ$ thresholds is the same as for non-interacting nucleons, gap bounds are sufficient to constrain nucleon-nucleon scattering amplitudes at phenomenologically relevant precision. Lanczos methods further reveal that energy-eigenstate estimates from previously studied asymmetric correlators have not converged over accessible imaginary times. Nevertheless, data-driven examples demonstrate why assumptions are required to draw conclusions about the natures of two-nucleon ground states at these masses.

Detmold, William [MIT, Cambridge, CTP]↗
DOE OSTI2025

Ground and excited state properties of ThBe and AcBe

In this work, the ground and excited states of ThBe and AcBe were investigated by performing high-level multireference and single-reference coupled-cluster quantum chemical calculations with large correlation consistent basis sets. Full potential energy curves (PECs), chemical bonding patterns, energetics, spectroscopic parameters (T e , r e , ω e , and ω e x e ), and spin–orbit effects of 13 and 8 electronic states of ThBe and AcBe, respectively, are reported. The ground electronic states of ThBe and AcBe are single-reference 1 3 Σ − (1σ 2 2σ 2 1π 2 ) and 1 2 Π (1σ 2 2σ 2 1π 1 ), respectively, and originate from their corresponding ground state fragments. The chemical bonding of ThBe (1 3 Σ − ) and AcBe (1 2 Π) are π-dative in character and are formed by d-electron transfers from Th/Ac to the empty 2p x and 2p y of the Be atom. The electron populations of the f-orbitals of both ThBe (1 3 Σ − ) and AcBe (1 2 Π) are minor which exhibit their “transition-metal-like” nature. The estimated bond energies of the spin–orbit ground states of ThBe (1 3 Σ − 0+ ) and AcBe (1 2 Π 1/2 ) are 12.79 and 11.02 kcal mol −1 , respectively. Finally, the bond energy of ThBe was used to estimate its heat of formation ΔH 0 f (298 K) of 869.61 ± 6 kJ mol −1 .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Final Results of the M AJORANA D EMONSTRATOR ’s Search for Double-Beta Decay of 76 Ge to Excited States of 76 Se

76 Ge can 𝛽⁢𝛽 decay into three possible excited states of 76 Se , with the emission of two or, if the neutrino is Majorana, zero neutrinos. None of these six transitions have yet been observed. The M AJORANA D EMONSTRATOR was designed to study 𝛽⁢𝛽 decay of 76 Ge using a low background array of high purity germanium detectors. With 98.2 kg-y of isotopic exposure, the demonstrator sets the strongest half-life limits to date for all six transition modes. For 2⁢𝜈⁢𝛽⁢𝛽 to the 0$^+_1$ state of 76 Se , this search has begun to probe for the first time half-life values predicted using modern many-body nuclear theory techniques, setting a limit of 𝑇 1/2 > 1.5 × 10 24 y (90% CL).

Majorana neutrinos↗
DOE OSTI2023

Excited-State Dynamics during Primary C–I Homolysis in Acetyl Iodide Revealed by Ultrafast Core-Level Spectroscopy

In typical carbonyl-containing molecules, bond dissociation events follow initial excitation to $nπ_{C=O}$$^*$ states. However, in acetyl iodide, the iodine atom gives rise to electronic states with mixed $nπ_{C=O}$$^*$ and $nπ_{C–I}$$^*$ character, leading to complex excited-state dynamics, ultimately resulting in dissociation. Using ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy and quantum chemical calculations, we present an investigation of the primary photodissociation dynamics of acetyl iodide via time-resolved spectroscopy of core-to-valence transitions of the I atom after 266 nm excitation. The probed I 4d-to-valence transitions show features that evolve on sub-100-fs time scales, reporting on excited-state wavepacket evolution during dissociation. These features subsequently evolve to yield spectral signatures corresponding to free iodine atoms in their spin–orbit ground and excited states with a branching ratio of 1.1:1 following dissociation of the C–I bond. Calculations of the valence excitation spectrum via equation-of-motion coupled cluster with single and double substitutions (EOM-CCSD) show that initial excited states are of spin-mixed character. From the initially pumped spin-mixed state, we use a combination of time-dependent density functional theory (TDDFT)-driven nonadiabatic ab initio molecular dynamics and EOM-CCSD calculations of the N$_{4,5}$ edge to reveal a sharp inflection point in the transient XUV signal that corresponds to rapid C–I homolysis. Here, by examining the molecular orbitals involved in the core-level excitations at and around this inflection point, we are able to piece together a detailed picture of C–I bond photolysis in which d → σ* transitions give way to d → p excitations as the bond dissociates. We also report theoretical predictions of short-lived, weak 4d → 5d transitions in acetyl iodide, validated by weak bleaching in the experimental transient XUV spectra. This joint experimental–theoretical effort has thus unraveled the detailed electronic structure and dynamics of a strongly spin–orbit coupled system.

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

Toward quantum computing for high-energy excited states in molecular systems: quantum phase estimations of core-level states

This paper explores the utility of the quantum phase estimation (QPE) in calculating high-energy excited states characterized by promotions of electrons occupying inner energy shells. These states have been intensively studied over the last few decades especially in supporting the experimental effort at light sources. Results obtained with the QPE are compared with various high-accuracy many-body techniques developed to describe core-level states. The feasibility of the quantum phase estimator in identifying classes of challenging shake-up states characterized by the presence of higher-order excitation effects is also discussed.

Bauman, Nicholas P.↗
DOE OSTI2026

Structure of high-lying excited states in 47 Ca with ℓ ≥ 3 populated in fast-beam 𝛾-ray-tagged one-neutron pickup reactions

Located just one neutron removed from doubly magic, stable 48 Ca, the adjacent isotope 47 Ca has been studied extensively with neutron-removing transfer reactions and interpreted within a shell-model picture. Neutron-adding transfer reactions onto the stable 46 Ca, however, have not been performed in nearly 60 years and never with the aid of high-resolution 𝛾-ray spectroscopy. Here, we report on the 12 C⁡( 46 , Ca 47 Ca+𝛾)⁢𝑋 one-neutron pickup reaction from 12 C onto 46 Ca at more than 50 MeV/nucleon, a regime of orbital angular momentum mismatch that selectively populates 47 Ca final states based on ℓ ≥ 3 neutron configurations. Newly observed excited states and 𝛾-ray transitions are discussed in comparison to 𝑓⁡𝑝 shell-model calculations in a variety of configuration spaces. Furthermore, it is shown that the nature of the observed spectrum of final states can be well interpreted, albeit with a significant fragmentation of the 𝜈⁢0⁢𝑓 5/2 strength observed in the measurement that is not borne out in the structure calculations.

39 ≤ A ≤ 58↗
DOE OSTI2023

Search for two-neutrino double-beta decay of 136 Xe to the $0$$^{+}_{1}$ excited state of 136 Ba with the complete EXO-200 dataset*

A new search for two-neutrino double-beta (2νββ) decay of 136 Xe to the $0$$^{+}_{1}$ excited state of 136 Ba is performed with the full EXO-200 dataset. A deep learning-based convolutional neural network is used to discriminate signal from background events. Signal detection efficiency is increased relative to previous searches by EXO-200 by more than a factor of two. With the addition of the Phase II dataset taken with an upgraded detector, the median 90% confidence level half-life sensitivity of 2νββ decay to the $0$$^{+}_{1}$ state of 136 Ba is 2.9 x 10 24 yr using a total 136 Xe exposure of 234.1 kg yr. Furthermore, no statistically significant evidence for 2νββ decay to the $0$$^{+}_{1}$ state is observed, leading to a lower limit of $T$$^{2v}_{1/2}$(0 + → $0$$^{+}_{1}$) > 1.4 x 10 24 yr at 90% confidence level, improved by 70% relative to the current world's best constraint.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

New measurement of double- β decays of Mo 100 to excited states of Ru 100 with the CUPID-Mo experiment

The CUPID-Mo experiment, located at Laboratoire Souterrain de Modane (France), was a demonstrator experiment for CUPID. It consisted of an array of 20 Li 2 100 MoO 4 (LMO) calorimeters each equipped with a Ge light detector (LD) for particle identification. In this work, we present the result of a search for two-neutrino and neutrinoless double beta decays of 100 Mo to the first 0 + and 2 + excited states of 100 Ru using the full CUPID-Mo exposure (2.71 kg yr of LMO). We measure the half-life of 2νββ decay to the $0^+_1$ state as $T^{2ν→0^+_1}_{1/2}$ = (7.5 ± 0.8 (stat.) $^{+0.4}_{-0.3}$ (syst.)) × 10 20 yr. The bolometric technique enables measurement of the electron energies as well as the gamma rays from nuclear de-excitation and this allows us to set new limits on the two-neutrino decay to the $2^+_1$ state of $T^{2ν→2^+_1}_{1/2}$ > 4.4×10 21 yr (90% c.i.) and on the neutrinoless modes of $T^{0ν→2^+_1}_{1/2}$ > 2.1×10 23 yr (90% c.i.), $T^{0ν→0^+_1}_{1/2}$ > 1.2 × 10 23 yr (90% c.i.). Information on the electrons spectral shape is obtained which allows us to make the first comparison of the single state (SSD) and higher state (HSD) 2νββ decay models for the $0^+_1$ excited state of 100 Ru.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Exciting DeePMD: Learning excited-state energies, forces, and non-adiabatic couplings

We extend the DeePMD neural network architecture to predict electronic structure properties necessary to perform non-adiabatic dynamics simulations. While learning the excited state energies and forces follows a straightforward extension of the DeePMD approach for ground-state energies and forces, how to learn the map between the non-adiabatic coupling vectors (NACV) and the local chemical environment descriptors of DeePMD is less trivial. Most implementations of machine-learning-based non-adiabatic dynamics inherently approximate the NACVs, with an underlying assumption that the energy-difference-scaled NACVs are conservative fields. We overcome this approximation, implementing the method recently introduced by Richardson [J. Chem. Phys. 158, 011102 (2023)], which learns the symmetric dyad of the energy-difference-scaled NACV. Furthermore, the efficiency and accuracy of our neural network architecture are demonstrated through the example of the methaniminium cation CH 2 NH 2 + .

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

Preparation of excited states for nuclear dynamics on a quantum computer

We study two different methods to prepare excited states on a quantum computer, a key initial step to study dynamics within linear response theory. The first method uses unitary evolution for a short time T = O(√1 - F) to approximate the action of an excitation operator Ô with fidelity F and success probability P ≈ 1 – F. The second method probabilistically applies the excitation operator using the Linear Combination of Unitaries (LCU) algorithm. We benchmark these techniques on emulated and real quantum devices, using a toy model for thermal neutron-proton capture. Despite its larger memory footprint, the LCU-based method is efficient even on current generation noisy devices and can be implemented at a lower gate cost than a naive analysis would suggest. Here, these findings show that quantum techniques designed to achieve good asymptotic scaling on fault tolerant quantum devices might also provide practical benefits on devices with limited connectivity and gate fidelity.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

An Ab Initio Multiple Cloning Method for Non-Adiabatic Excited-State Molecular Dynamics in NWChem

The recently developed ab-initio multiple cloning (AIMC) approach based on the multicongurational Ehrenfest (MCE) method provides a powerful and accurate way of describing the excited-state dynamics of molecular systems. The AIMC method is a controlled approximation to non-adiabatic dynamics with a particular strength in the proper description of decoherence effects due to branching of vibrational wavepackets at a level crossing. In this work, we report a new implementation of the AIMC algorithm in the open source NWChem computational chemistry program. The framework combines linear-response time-dependent density functional theory with Ehrenfest mean-eld theory to determine the equations of motion for classical trajectories. The multi-dimensional wave function is decomposed into a superposition of Gaussian coherent states guided by Ehrenfest trajectories (i.e., MCE approach), which can clone with fully quantum mechanical amplitudes and phases. By using an efficient time-derivative based non-adiabatic coupling approach within the AIMC method, all observable are calculated on-the-y in the non-adiabatic molecular dynamics process. As a representative example, we apply our implementation to study the ultrafast photoinduced electronic and vibrational energy transfer in a pyridine molecule. The effects of the cloning procedure on electronic and vibrational coherence, relaxation and unidirectional energy transfer are discussed. This new AIMC implementation provides a high-level non-adiabatic molecular dynamics framework for simulating photoexcited dynamics in complex molecular systems and experimentally relevant ultrafast spectroscopic probes, such as nonlinear coherent optical and X-ray signals.

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

Size-Transferable Prediction of Excited State Properties for Molecular Assemblies with a Machine Learning Exciton Model

Computational modeling of the excited states of molecular aggregates faces significant computational challenges and size heterogeneity. Current machine learning (ML) models, typically trained on specific-sized aggregates, struggle with scalability. We found that the exciton model Hamiltonian of large aggregates can be decomposed into dimer pairs, allowing an ML model trained on dimers to reconstruct Hamiltonians for aggregates of any size. We also proposed a new method to address the phase-correction problem by introducing coupling terms’ approximations. Our model accurately predicted the excitation energies of the trimer and tetramer of perylene and tetracene and estimated S1 oscillator strengths of perylene aggregates. Leveraging our ML model, the optical gaps of nanosized perylene aggregates with up to 50 monomers are analyzed, qualitatively revealing the role of different couplings on their size dependency. Future work will explore transferability across different monomers to predict optical properties in heterogeneous assemblies.

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

Benchmarking third-order cluster perturbation theory for electronically excited states

In this study, we investigate the reliability of cluster perturbation (CP) theory applied to the calculation of electronically excited states through a comprehensive benchmark. In CP theory, perturbative corrections are added to the properties of a parent excitation space, which converge toward the properties of a target excitation space. For the CPS(D-n) model, perturbative corrections through order n are added to the coupled cluster singles (CCS) excitation energies to target the coupled cluster singles and doubles (CCSD) excitation energies. Through a comparative analysis of excitation energy calculations across a diverse set of molecules and wavefunction methods, we present a comprehensive evaluation of the accuracy of the third-order CPS(D) model, CPS(D-3), in calculating excitation energies. Further, our findings demonstrate that CPS(D-3) is a reliable alternative to established methods, particularly CCSD, while systematically overestimating the excitation energies compared to high-level coupled cluster methods such as CC3. These results highlight the strengths and limitations of CPS(D-3), as well as the promising directions for its future development.

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

Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra

Green’s function methods within many-body perturbation theory provide a general framework for treating electronic correlations in excited states and spectra. Conventional methods using the Dyson equation or the cumulant expansion are typically based on the GW self-energy approximation. In order to extend this approximation in molecular systems, a non-perturbative real-time coupled-cluster cumulant Green’s function approach has been introduced, where the cumulant is obtained as the solution to a set of coupled first order, non-linear differential equations. This approach naturally includes non-linear corrections to conventional cumulant Green’s function techniques where the cumulant is linear in the GW self-energy. The method yields the spectral function associated with the core Green’s function, which is directly related to the x-ray photoemission spectra (XPS) of molecular systems. The approach also yields very good results for binding energies and satellite excitations. The x-ray absorption spectrum (XAS) is then obtained as a convolution of the core spectral function and an effective one-body absorption spectrum. Here this approach is extended to include the full coupled-cluster-singles (CCS) core Green’s function by including the complete form of the non-linear contributions to the cumulant as well as all single, double, and triple cluster excitations in the CC amplitude equations. This approach naturally builds in orthogonality and shake-up effects analogous to those in the Mahan-Noizeres-de Dominicis edge singularity corrections that enhance the XAS near the edge. Themethod is illustrated for the XPS and XAS of NH 3 .

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

Extracting doubly excited state lifetimes in helium directly in the time domain with attosecond noncollinear four-wave-mixing spectroscopy

The helium atom, with one nucleus and two electrons, is a prototypical system to study quantum many-body dynamics. Doubly excited states, or quantum states in which both electrons are excited by one photon, showcase electronic-correlation mediated effects. In this paper, the natural lifetimes of the doubly excited 1 P o 2 s n p Rydberg series and the 1 S e 2 p 2 dark state in helium in the 60–65 eV region are measured directly in the time domain with extreme-ultraviolet/near-infrared noncollinear attosecond four-wave-mixing (FWM) spectroscopy. The measured lifetimes agree with lifetimes deduced from spectral linewidths and theoretical predictions, and the roles of specific decay mechanisms are considered. While complex spectral line shapes in the form of Fano resonances are common in absorption spectroscopy of autoionizing states, the background-free and thus homodyned character of noncollinear FWM results exclusively in Lorentzian spectral features in the absence of strong-field effects. The onset of strong-field effects that would affect the extraction of accurate natural lifetimes in helium by FWM is determined to be approximately 0.3 Rabi cycles. This study provides a systematic understanding of the FWM parameters necessary to enable accurate lifetime extractions, which can be utilized in more complex quantum systems in the future. Published by the American Physical Society 2024

Rupprecht, Patrick (ORCID:000000026491793X)↗
DOE OSTI2020

Results of the MAJORANA DEMONSTRATOR’s Search for Double-Beta Decay of 76 Ge to Excited States of 76 Se

The MAJORANA DEMONSTRATOR is searching for double-beta decay of 76 Ge to excited states (E.S.) in 76Se using a modular array of high purity Germanium detectors. 76 Ge can decay into three E.S.s of 76 Se. The E.S. decays have a clear event signature consisting of a ββ-decay with the prompt emission of one or two γ-rays, resulting in with high probability in a multi-site event. The granularity of the DEMONSTRATOR detector array enables powerful discrimination of this event signature from backgrounds. Using 21.3 kg-y of isotopic exposure, the DEMONSTRATOR has set world leading limits for each E.S. decay, with 90% CL lower half-life limits in the range of (0.56 – 2.1) • 10 24 y. In particular, for the 2v transition to the first 0 + E.S. of 76 Se, a lower half-life limit of 0.68 • 10 24 at 90% CL was achieved.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗