Search NASA⌕ Search

SEARCH · Search NASA

Results for “Excited states method”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Wilson loops with neural networks

Wilson loops are essential objects in QCD and have been pivotal in scale setting and demonstrating confinement. Various generalizations are crucial for computations needed in effective field theories. In lattice gauge theory, Wilson loop calculations face challenges, including excited-state contamination at short times and the signal-to-noise ratio issue at longer times. To address these problems, we develop a new method by using neural networks to parametrize interpolators for the static quark-antiquark pair. We construct gauge-equivariant layers for the network and train it to find the ground state of the system. The trained network itself is then treated as our new observable for the inference. Our results demonstrate a significant improvement in the signal compared to traditional Wilson loops, performing as well as Coulomb-gauge Wilson-line correlators while maintaining gauge invariance. Additionally, we present an example where the optimized ground state is used to measure the static force directly, as well as another example combining this method with the multilevel algorithm. Finally, we extend the formalism to find excited-state interpolators for static quark-antiquark systems. To our knowledge, this work is the first study of neural networks with a physically motivated loss function for Wilson loops.

Bellscheidt, Verena [Massachusetts Inst. of Techno↗
DOE OSTI2025

Modeling Charge Transfer Excitation with Variation After Response Quantum Monte Carlo (Final Technical Report)

The electronically excited states of molecules play critical roles both in spectroscopy and in technological application, ranging from UV/Vis absorption experiments to the production of solar fuels. However, certain types of excitations, such as charge transfer excitations, remain difficult to treat with existing methods such as time dependent density functional theory or linear response coupled cluster. Under this Early Career Research Award, we developed a number of different theoretical methods to address this issue, which began with Variational Monte Carlo methods and branched into multiple types of excited-state-specific quantum chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1977

Transient excitation and mechanical admittance test techniques for prediction of payload vibration environments

Transient excitation forces were applied separately to simple beam-and-mass launch vehicle and payload models to develop complex admittance functions for the interface and other appropriate points on the structures. These measured admittances were then analytically combined by a matrix representation to obtain a description of the coupled system dynamic characteristics. Response of the payload model to excitation of the launch vehicle model was predicted and compared with results measured on the combined models. These results are also compared with results of earlier work in which a similar procedure was employed except that steady-state sinusoidal excitation techniques were included. It is found that the method employing transient tests produces results that are better overall than the steady state methods. Furthermore, the transient method requires far less time to implement, and provides far better resolution in the data. However, the data acquisition and handling problem is more complex for this method. It is concluded that the transient test and admittance matrix prediction method can be a valuable tool for development of payload vibration tests.

Kana, D. D.↗
DOE OSTI2025

Simulation of 24,000 Electron Dynamics: Real-Time Time-Dependent Density Functional Theory (TDDFT) with the Real-Space Multigrids (RMG)

Here, we present the theory, implementation, and benchmarking of a real-time time-dependent density functional theory (RT-TDDFT) module within the RMG code, designed to simulate the electronic response of molecular systems to external perturbations. Our method offers insights into nonequilibrium dynamics and excited states across a diverse range of systems, from small organic molecules to large metallic nanoparticles. Benchmarking results demonstrate excellent agreement with established TDDFT implementations and showcase the superior stability of our time integration algorithm, enabling long-term simulations with minimal energy drift. The scalability and efficiency of RMG on massively parallel architectures allow for simulations of complex systems, such as plasmonic nanoparticles with thousands of atoms. Future extensions, including nuclear and spin dynamics, will broaden the applicability of this RT-TDDFT implementation, providing a powerful toolset for studies of photoactive materials, nanoscale devices, and other systems where real-time electronic dynamics is essential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1977

Line strengths, collision strengths and excitation rates for multiply-charged silicon ions

In the present paper, the line strengths, collision strengths, and rate coefficients are calculated for a variety of transitions in multiply charged silicon ions from Si(VI) to Si(XIV). The line strengths are obtained by using Clementi wave functions for the ground-state configuration, and excited-state wave functions generated by a semiempirical method. The collision strengths are calculated in an LS coupling scheme in the distorted-wave approximation, neglecting exchange except for the helium-like transitions. These results are then integrated over a Maxwellian velocity distribution function to yield rate coefficients. The rates are presented graphically and also in terms of a two-parameter fit.

Davis, J.↗
NASA NTRS1980

Efficient ionisation of calcium, strontium and barium by resonant laser pumping

Efficient ionization has been observed when an atomic vapor of strontium, barium or calcium was illuminated with a long pulse tunable laser at the frequency of the atomic resonance line. The variation in the degree of ionization with neutral density and laser intensity has been measured using the 'hook' method. The maximum ionization observed was 94%. Excited state populations were measured yielding an excitation temperature (depending on exact experimental conditions) in the region of 0.4 eV. The decay of ion density after the laser pulse was monitored and the recombination coefficients determined. The results are interpreted in terms of an electron heating model.

Skinner, C. H.↗
NASA NTRS1990

Non-linear dynamics of a spur gear pair

The backlash nonlinearity excited primarily by transmission error between spur gear pairs is studied for both external and internal excitations. The digital simulation technique and the method of harmonic balance are used to develop steady state solutions for the internal sinuosidal excitations. The analytic predictions agreed well with available experimental data. Digital simulation is used to observe that at the chaotic and subharmonic resonances may exist in a gear pair depending on the mean or design load, mean to alternating force ratio, damping, and backlash.

Kahraman, A.↗
DOE OSTI2026

Low-Lying Excited States of Linear All- Trans Polyenes: Insights from Analytic Gradient and Nonadiabatic Coupling Calculations Based on Multireference Configuration Interaction

Polyenes serve as a rigorous test for theoretical models and electronic structure methods, playing a key role in advancing computational and theoretical chemistry. Here, we present a high-level theoretical investigation of linear, all-trans polyenes using energy gradients and nonadiabatic coupling vectors based on an MR-CISD wave function to describe electronic transitions involving the ground state (1 1 A g – ) and three low-lying excited states (2 1 A g – , 1 1 B u + , and 2 1 B u – ) of hexatriene, octatetraene, and decapentaene. This approach enables accurate evaluation of both adiabatic and vertical excitation and emission energies, yielding results in excellent agreement with experiment, as well as locating minima on the crossing seam between adiabatic states. Our results show that vertical excitation energies to the 1 1 B u + state are blue-shifted by 0.2–0.3 eV relative to the experimental absorption maximum, whereas the vertical emission energy from the 2 1 A g – state is red-shifted by ∼0.2 eV relative to the experimental emission maximum. Upon relaxation from the Franck–Condon geometry, the 2 1 A g – state stabilizes by around 1 eV, compared to 0.2–0.3 eV for the 1 1 B u + state. An analysis of the S 1 /S 0 crossing seam in hexatriene shows that its minimum involves asymmetric backbone deformations and provides an efficient channel for ultrafast internal conversion to the ground state, consistent with the absence of detectable fluorescence in this molecule. These results demonstrate the power of analytic gradients and nonadiabatic coupling vectors based on an MR-CISD wave function for accurately characterizing the electronic structure and photophysics of polyenes.

Excited states↗
DOE OSTI2026

Hot-Carrier Injection and Millisecond Charge Separation from a Robust Heteroleptic Iron(II) Chromophore Immobilized on TiO 2

The synthesis, spectroscopic characterization, computational analysis, and photoelectrochemical behavior of a new iron-based chromophore, [(Cpy) 2 Fe- (deeb)](PF 6 ) 2 (Fe(Cpy) 2 (deeb)), where Cpy is 1-methyl-3-(2-pyridyl)imidazole and deeb is 4,4’-(CO 2 CH 2 CH 3 ) 2 -2,2’-bipyridine, is reported. Electrochemically reversible waves assigned to a metal-centered E o (Fe III/II ) = +0.48 and a ligand-centered E o (Fe 2+/+ ) = −1.47 V vs Fc +/0 reduction were evident in cyclic voltammetry measurements. The combination of a strong σ-donor and a π-acceptor lowered the energy of the metal-toligand charge-transfer (MLCT) excited state relative to the metal-centered state. Two MLCT transitions appear in the visible region at 424 and 580 nm. TDDFT calculations revealed that the lower-energy band was well formulated as Fe(II)→deeb, and the higher-energy transition was charge transfer to both the deeb and Cpy ligands. Resonance Raman spectroscopy supports these findings showing enhanced deeb vibrational modes with 532 nm excitation, both deeb and Cpy modes with 473 nm excitation, and exclusively Cpy with 405 nm excitation. Ultrafast spectroscopy reveals a short-lived (∼2 ps) MLCT excited state and a longer-lived (∼20 ps) metal-centered state. Efficient methods to deprotect the ester groups and anchor the complex to mesoporous TiO 2 (anatase) thin films in high surface coverages, Fe(Cpy) 2 (dcb)|TiO 2 σ = 3 × 10 −8 mol/cm 2 , were established. Pulsed light excitation of Fe(Cpy) 2 (dcb)|TiO 2 resulted in rapid excited state injection (k inj > 10 8 s −1 ) and formation of a charge-separated state, Fe III (Cpy) 2 (dcb)|TiO 2 (e), which persists on the millisecond time scale before returning cleanly to the ground state with secondorder kinetics. Injection yields measured 50 ns after light excitation were found to double from Φ = 0.15 with green (532 nm) light to 0.30 with blue (457 nm) light excitation. Incident photon-to-current efficiency (% IPCE) measurements as a function of excitation wavelength in a 0.5 M LiI/I 2 /CH 3 CN electrolyte provide clear evidence for band-selective “hot carrier” injection from the remote Cpy-localized excited state. Collectively, the spectroscopic and photoelectrochemical data indicate that a semiconductor can intercept hot electrons from iron chromophores even when the excited-state dipole is oriented away from the surface-anchoring ligand.

Charge transfer↗
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

Alternant Hydrocarbon Diradicals as Optically Addressable Molecular Qubits

High-spin molecules allow for bottom-up qubit design and are promising platforms for magnetic sensing and quantum information science. Optical addressability of molecular electron spins has also been proposed in first-row transition-metal complexes via optically detected magnetic resonance (ODMR) mechanisms analogous to the diamond-nitrogen-vacancy color center. However, significantly less progress has been made on the front of metal-free molecules, which can deliver lower costs and milder environmental impacts. At present, most luminescent open-shell organic molecules are π-diradicals, but such systems often suffer from poor ground-state open-shell characters necessary to realize a stable ground-state molecular qubit. In this work, we use alternancy symmetry to selectively minimize radical–radical interactions in the ground state, generating π-systems with high diradical characters. We call them m-dimers, referencing the need to covalently link two benzylic radicals at their meta carbon atoms for the desired symmetry. Through a detailed electronic structure analysis, we find that the excited states of alternant hydrocarbon m-diradicals contain important symmetries that can be used to construct ODMR mechanisms leading to ground-state spin polarization. Furthermore, the molecular parameters are set in the context of a tris(2,4,6-trichlorophenyl)methyl (TTM) radical dimer covalently tethered at the meta position, demonstrating the feasibility of alternant m-diradicals as molecular color centers.

Chemistry↗
DOE OSTI2026

Decay spectroscopy in the neutron-rich Mo–Ru–Pd region

A leading challenge of nuclear-structure research is to understand the properties of nuclides of extreme isospin. Experiments at radioactive-ion-beam facilities, such as the Facility for Rare Isotope Beams in the US, may answer key questions that address diverse topics including fundamental nuclear physics, stellar nucleosynthesis and nuclear applications. The neutron-rich Mo–Ru–Pd (Z = 42 – 46) nuclides are hypothesised to exhibit triaxial-oblate deformation. We performed an experiment with the Facility for Rare Isotope Beams Decay Station initiator (FDSi) to study the structure and decay properties of nuclides in this region. Over 100 different nuclides have been identified in a preliminary analysis of the data. This work presents a first look at several examples between Rb (Z = 37) and Ag (Z = 47). Performance of the FDSi and methods developed to measure ground-state and excited-state lifetimes are presented, and plans for future work are also discussed.

Allmond, James [ORNL] (ORCID:0000000165338721)↗
NASA NTRS1990

Active control synthesis for flexible space structures excited by persistent disturbances

Both classical and state-space synthesis methods for active control of flexible space structures in the presence of persistent disturbances are presented. The methods exploit the so-called internal model principle for asymptotic disturbance rejection. A generic example of flexible space structures is used to illustrate the simplicity of the proposed design methodologies. The concept of a disturbance rejection filter dipole is introduced from a classical control viewpoint. It is shown that the proposed design methods will invariably make use of non-minimum-phase compensation for a class of noncolocated control problems. The need for tradeoffs between performance and parameter robustness is discussed.

Wie, Bong↗
DOE OSTI2025

Characterizing the Excited States and Electronic Absorption Spectra of Small Alkylperoxy (RO 2 •) and Hydroperoxy (•QOOH) Radicals

Organic peroxy (ROO•) and hydroperoxy (•QOOH) radicals are key reactive intermediates that are formed via the oxidation of volatile organic compounds during combustion or in the Earth’s atmosphere. Their primary fate is continued unimolecular decay or bimolecular chemistry, the relative branching for which is heavily structure- and temperature-dependent. This article outlines a combined single- and multi-reference quantum chemical study to characterize the near-UV accessible electronically excited states of the prototypical ROO• and •QOOH intermediates, tert-butyl peroxy and hydroperoxy-tert-butyl radicals—the ground-state chemistries of which have been well studied both experimentally and computationally. Additionally, we simulate the electronic absorption profiles of these ROO• and •QOOH intermediates with a variety of multi- and single-reference methods. The results show an interesting conformer dependence on the electronically excited-state character and electronic absorption maxima of •QOOH. The results show promise for electronic absorption spectroscopy to be used as a selected probe for determining •QOOH conformers. Additionally, electronic absorption may contribute to the daytime removal of long-lived •QOOH intermediates formed in the troposphere. We expect that our studies will motivate experiments on the electronic absorption spectra of experimentally achievable ROO• and •QOOH.

excited states↗
DOE OSTI2026

Lifetimes of two- and four-neutron-hole states in 204 Pb and 206 Pb

The centroid-shift method was used to determine half-lives of excited levels in 204 Pb and 206 Pb. For the states with 𝐼 𝜋 = 12 + , 17 − , and 19 − in 204 Pb, values of 𝑇 1/2 = 4.9⁢(3), 3.9(3), and 0.9(3) ns, respectively, were determined. The half-life of the 𝐼 𝜋 = 9 − level in 206 Pb was measured to be 1.1(3) ns. In 204 Pb, the 12 + state arises from two neutron holes in the 𝑖 13/2 subshell, while the 17 − and 19 − levels are built on 𝜈⁡(𝑖$^{−3}_{13/2}$, 𝑝$^{−1}_{1/2}$) and 𝜈⁡(𝑖$^{−3}_{13/2}$, 𝑓$^{−1}_{5/2}$) four-neutron-hole configurations, respectively. The 9 − state in 206 Pb results from a 𝜈⁡(𝑖$^{−1}_{13/2}$, 𝑓${−1}_{5/2}$) excitation. As a result, the transition probabilities for the decay of these isomeric levels are reasonably consistent with the expected single-particle values, and these states are described well by shell-model calculations using the kshell code with the KHHE interaction.

190 ≤ A ≤ 219↗
DOE OSTI2024

Quantum-enhanced photoprotection in neuroprotein architectures emerges from collective light-matter interactions

Background Superradiance is the phenomenon of many identical quantum systems absorbing and/or emitting photons collectively at a higher rate than any one system can individually. This phenomenon has been studied analytically in idealized distributions of electronic two-level systems (TLSs), each with a ground and excited state, as well as numerically in realistic photosynthetic nanotubes and cytoskeletal architectures. Methods Superradiant effects are studied here in idealized toy model systems and realistic biological mega-networks of tryptophan (Trp) molecules, which are strongly fluorescent amino acids found in many proteins. Each Trp molecule acts as a chromophore absorbing in the ultraviolet spectrum and can be treated approximately as a TLS, with its 1 L a excited singlet state; thus, organized Trp networks can exhibit superradiance. Such networks are found, for example, in microtubules, actin filaments, and amyloid fibrils. Microtubules and actin filaments are spiral-cylindrical protein polymers that play significant biological roles as primary constituents of the eukaryotic cytoskeleton, while amyloid fibrils have been targeted in a variety of neurodegenerative diseases. We treat these proteinaceous Trp networks as open quantum systems, using a non-Hermitian Hamiltonian to describe interactions of the chromophore network with the electromagnetic field. We numerically diagonalize the Hamiltonian to obtain its complex eigenvalues, where the real part is the energy and the imaginary part is its associated enhancement rate. We also consider multiple realizations of increasing static disorder in either the site energies or the decay rates. Results We obtained the energies and enhancement rates for realistic microtubules, actin filament bundles, and amyloid fibrils of differing lengths, and we use these values to calculate the quantum yield, which is the ratio of the number of photons emitted to the number of photons absorbed. We find that all three of these structures exhibit highly superradiant states near the low-energy portion of the spectrum, which enhances the magnitude and robustness of the quantum yield to static disorder and thermal noise. Conclusion The high quantum yield and stable superradiant states in these biological architectures may play a photoprotective rolein vivo, downconverting energetic ultraviolet photons—absorbed from those emitted by reactive free radical species—to longer, safer wavelengths and thereby mitigating biochemical stress and photophysical damage. Contrary to conventional assumptions that quantum effects cannot survive in large biosystems at high temperatures, our results suggest that macropolymeric collectives of TLSs in microtubules, actin filaments, and amyloid fibrils exhibit increasingly observable and robust effects with increasing length, up to the micron scale, due to quantum coherent interactions in the single-photon limit. Superradiant enhancement and high quantum yield exhibited in neuroprotein polymers could thus play a crucial role in information processing in the brain, the development of neurodegenerative diseases such as Alzheimer’s and related dementias, and a wide array of other pathologies characterized by anomalous protein aggregates.

Physics↗
DOE OSTI2024

Strategies to Obtain Reliable Energy Landscapes from Embedded Multireference Correlated Wavefunction Methods for Surface Reactions

Embedded correlated wavefunction (ECW) theory is a powerful tool for studying ground- and excited-state reaction mechanisms and associated energetics in heterogeneous catalysis. Several factors are important to obtaining reliable ECW energies, critically the construction of consistent active spaces (ASs) along reaction pathways when using a multireference correlated wavefunction (CW) method that relies on a subset of orbital spaces in the configuration interaction expansion to account for static electron correlation, e.g., complete AS self-consistent field theory, in addition to the adequate partitioning of the system into a cluster and environment, as well as the choice of a suitable basis set and number of states included in excited-state simulations. Here, in this work, we conducted a series of systematic studies to develop best-practice guidelines for ground- and excited-state ECW theory simulations, utilizing the decomposition of NH 3 on Pd(111) as an example. We determine that ECW theory results are relatively insensitive to cluster size, the aug-cc-pVDZ basis set provides an adequate compromise between computational complexity and accuracy, and that a fixed-clean-surface approximation holds well for the derivation of the embedding potential. Additionally, we demonstrate that a merging approach, which involves generating ASs from the molecular fragments at each configuration, is preferable to a creeping approach, which utilizes ASs from adjacent structures as an initial guess, for the generation of consistent potential energy curves involving open-d-shell metal surfaces, and, finally, we show that it is essential to include bands of excited states in their entirety when simulating excited-state reaction pathways.

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