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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Nonadiabatic Derivative Couplings through Multiple Franck–Condon Modes Dictate the Energy Gap Law for Near and Short-Wave Infrared Dye Molecules

Near infrared (NIR, 700–1000 nm) and short-wave infrared (SWIR, 1000–2000 nm) dye molecules exhibit significant nonradiative decay rates from the first singlet excited state to the ground state. While these trends can be empirically explained by a simple energy gap law, detailed mechanisms of nearly universal behavior have remained unsettled for many cases. Theoretical and experimental results for two representative NIR/SWIR dye molecules reported here clarify the key mechanism for the observed energy gap law behavior. It is shown that the first derivative nonadiabatic coupling terms serve as major coupling pathways for nonadiabatic decay processes from the first excited singlet state to the ground state for these NIR and SWIR dye molecules and that vibrational modes other than the highest frequency modes also make significant contributions to the rate. Finally, this assessment is corroborated by further theoretical comparison with possible alternative mechanisms of intersystem crossing to triplet states and also by comparison with experimental data for deuterated molecules.

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

Symmetry dilemmas in quantum computing for chemistry: A comprehensive analysis

Symmetry adaptation, universality, and gate efficiency are central but often competing requirements in quantum algorithms for electronic structure and many-body physics. For example, fully symmetry-adapted universal operator pools typically generate long and deep quantum circuits; gate-efficient universal operator pools generally break symmetries; and gate-efficient, fully symmetry-adapted operator pools may not be universal. In this work, we analyze such symmetry dilemmas both theoretically and numerically. On the theory side, we prove that the popular, gate-efficient operator pool consisting of singlet spin-adapted singles and perfect-pairing doubles is not universal when spatial symmetry is enforced. To demonstrate the strengths and weaknesses of the three types of pools, we perform numerical simulations using an adaptive algorithm paired with operator pools that are (i) fully symmetry-adapted and universal, (ii) fully symmetry-adapted and non-universal, and (iii) breaking a single symmetry and universal. Our numerical simulations encompass three physically relevant scenarios in which the target state is (i) the global ground state, (ii) the ground state crossed by a state differing in multiple symmetry properties, and (iii) the ground state crossed by a state differing in a single symmetry property. Our results show when symmetry-breaking but universal pools can be used safely, when enforcing at least one distinguishing symmetry suffices, and when a particular symmetry must be rigorously preserved to avoid variational collapse. Together, the formal and numerical analyses provide a practical guide for designing and benchmarking symmetry-adapted operator pools that balance universality, resource requirements, and robust state targeting in quantum simulations for chemistry.

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

Nonadiabatic couplings from a variational excited state method based on constrained DFT

Excited Costrained Density Functional Theory (XCDFT) is a variational excited state method that extends ground state DFT to the computation of low-lying excited states. It borrows much of the machinery of Constrained DFT (CDFT) with a crucial difference: the constraint imposes a population of one electron in the Hilbert space spanned by the virtuals of a reference ground state. Here, we present theory and implementation for evaluating nonadiabatic coupling vectors (NACVs) between the first excited state computed with XCDFT and the ground state. Our NACVs are computed analytically using density functional perturbation theory with a formalism that is general enough that could be applied to CDFT diabatic states. We showcase the new method with pilot NACV calculations for the conical intersection in H 3 , the avoided crossing in selenoacrolein, and the NACV magnitudes in azobenzene. Despite complications from the nonorthogonality of the wavefunctions, XCDFT’s energy surfaces and NACVs reproduce benchmark values and respect known sum rules within a reasonable degree. This shows that XCDFT is a viable method for nonadiabatic dynamics simulations.

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

Ultrafast population and structural dynamics of a Ni-bipyridine photoredox catalyst reveal a significant deactivation pathway

The ultrafast excited state pathways and dynamics of NiII-bipyridine complexes influence the yield of photochemical processes involved in their catalytic cross-coupling reactions. Here we present ultrafast Ni K x-ray emission spectroscopy (XES) and x-ray solution scattering (XSS) of a NiII-bipyridine aryl halide complex, [Ni(t-Bubpy)(o-tol)Br], to quantify the excited state population dynamics and structural changes of the pre-catalyst. Due to the local spin-sensitivity of XES, the population dynamics of metal-to-ligand charge transfer (MLCT) and metal-centered (MC) excited states is established. A rapid ground state recovery pathway is newly identified, representing a significant deactivation pathway during photocatalysis. Furthermore, the pseudotetrahedral structure of the long-lived MC excited state is unambiguously identified and refined by XSS. The results advance our understanding of the ultrafast relaxation mechanisms that impact the photocatalytic mechanism and yield for NiII-bipyridine aryl halide cross-coupling catalysts.

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

Atomic ionization: sd energy imbalance and Perdew–Zunger self-interaction correction energy penalty in 3d atoms

To accurately describe the energetics of transition metal systems, density functional approximations (DFAs) must provide a balanced description of s- and d- electrons. One measure of this is the sd transfer error, which has previously been defined as E ( 3 d n − 1 4 s 1 ) − E ( 3 d n − 2 4 s 2 ) . Theoretical concerns have been raised about this definition due to its evaluation of excited-state energies using ground-state DFAs. A more serious concern appears to be strong correlation in the 4s 2 configuration. Here, we define a ground-state measure of the sd energy imbalance, based on the errors of s- and d-electron second ionization energies of the 3d atoms, that effectively circumvents the aforementioned problems. We find an improved performance as we move from the local spin density approximation (LSDA) to the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) to the regularized and restored Strongly Constrained and Appropriately Normed (r 2 SCAN) meta-GGA for first-row transition metal atoms. However, we find large (∼2 eV) ground-state sd energy imbalances when applying a Perdew–Zunger 1981 self-interaction correction. This is attributed to an “energy penalty” associated with the noded 3d orbitals. A local scaling of the self-interaction correction to LSDA results in a balance of s- and d-errors.

Science & Technology - Other Topics↗
DOE OSTI2021

Electron–phonon interaction in Kondo lattice systems

Highlights: • Rigorous study of ground state properties of the Kondo lattice model with an electron–phonon. • The ground state is proved to be unique. • The total spin of the ground state is determined according to the lattice structure. • Novel applications of order preserving operator inequalities. We study ground state properties of the Kondo lattice model with an electron–phonon interaction. The ground state is proved to be unique; in addition, the total spin of the ground state is determined according to the lattice structure. To prove the assertions, an extension of the method of spin reflection positivity is given in terms of order preserving operator inequalities.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Improving the accuracy and efficiency of quantum connected moments expansions

The still-maturing noisy intermediate-scale quantum technology faces strict limitations on the algorithms that can be implemented efficiently. In the realm of quantum chemistry, the variational quantum eigensolver (VQE) algorithm has become ubiquitous, with many variations. Alternatively, a promising new avenue has been unraveled by the quantum variants of techniques grounded on expansions of the moments of the Hamiltonian, notably the connected moments expansion (CMX) and the Peeters–Devreese–Soldatov (PDS) energy functional. Common to those approaches is that, upon preparing an approximate ground state used to compute the necessary moments, the accuracy of the estimated ground state energy depends on the degree of overlap between the prepared state and the true ground state. Thus, we use the ADAPT-VQE algorithm to test shallow circuit construction strategies for the purpose of increasing the overlap with the exact ground state, validated by the sizable accuracy improvement herein reported in the PDS and CMX ground state energies. We also show that we can take advantage of the fact that the terms to be measured are highly recurring in different moments, incurring a substantial reduction in the number of necessary measurements. Finally, by coupling this measurement caching with a threshold that determines whether a given term is to be measured based on its associated scalar coefficient, we observe a further reduction in the number of circuit implementations while allowing for tunable accuracy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Strategies for Computer-Aided Discovery of Novel Open-Shell Polymers

Organic π-conjugated polymers with a triplet ground state have been the focus of recent research for their interesting and unique electronic properties, arising from the presence of the two unpaired electrons. These compounds are usually built from alternating electron-donating and electron-accepting monomer pairs which lower the HOMO–LUMO gap and yield a triplet state instead of the typical singlet ground state. In this paper, we use density functional theory calculations to explore the design rules that govern the creation of a ground-state triplet conjugated polymer and find that a small HOMO–LUMO gap in the singlet state is the best predictor for the existence of a triplet ground state, compared to previous use of a pro-quinoidal bonding character. Furthermore, this work can accelerate the discovery of new stable triplet materials by reducing the computational resources needed for electronic-state calculations and the number of potential candidates for synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Transition width of the of the $J$ $π$ = $1$ – two-phonon state of $88$ $Sr$

The ground-state decay width of the two-phonon $J$ $π$ = $1$ – , 4742 keV state of 88 Sr has been determined with the relative self-absorption method combined with a monoenergetic photon beam. This width is important to determine the decay transition strengths into the ground state and the one-phonon $2$$^{+}_{1}$ and $3$$^{–}_{1}$ levels which are required to verify the two-phonon character of the $J$ $π$ = $1$ – state. Here, the experiment was performed at the High Intensity γ-ray Source (HI⁢ γ⁢S) using a novel experimental approach to adapt the relative self-absorption method to monoenergetic photon beams. The result for the ground-state decay width is, thus, independent of any calibration standard and confirms the two-phonon character of the 88 Sr, $J$ $π$ = $1$ – , 4742 keV state within an improved uncertainty.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Simulations of frustrated Ising Hamiltonians using quantum approximate optimization

Novel magnetic materials are important for future technological advances. Theoretical and numerical calculations of ground-state properties are essential in understanding these materials, however, computational complexity limits conventional methods for studying these states. Here we investigate an alternative approach to preparing materials ground states using the quantum approximate optimization algorithm (QAOA) on near-term quantum computers. We study classical Ising spin models on unit cells of square, Shastry-Sutherland and triangular lattices, with varying field amplitudes and couplings in the material Hamiltonian. We find relationships between the theoretical QAOA success probability and the structure of the ground state, indicating that only a modest number of measurements (≲100) are needed to find the ground state of our nine-spin Hamiltonians, even for parameters leading to frustrated magnetism. We further demonstrate the approach in calculations on a trapped-ion quantum computer and succeed in recovering each ground state of the Shastry-Sutherland unit cell with probabilities close to ideal theoretical values. The results demonstrate the viability of QAOA for materials ground state preparation in the frustrated Ising limit, giving important first steps towards larger sizes and more complex Hamiltonians where quantum computational advantage may prove essential in developing a systematic understanding of novel materials.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Photofragment imaging differentiates between one- and two-photon dissociation pathways in MgI+

The bond strength and photodissociation dynamics of MgI+ are determined by a combination of theory, photodissociation spectroscopy, and photofragment velocity map imaging. From 17 000 to 21 500 cm−1, the photodissociation spectrum of MgI+ is broad and unstructured; photofragment images in this region show perpendicular anisotropy, which is consistent with absorption to the repulsive wall of the (1) Ω = 1 or (2) Ω = 1 states followed by direct dissociation to ground state products Mg+ (2S) + I (2P3/2). Analysis of photofragment images taken at photon energies near the threshold gives a bond dissociation energy D0(Mg+-I) = 203.0 ± 1.8 kJ/mol (2.10 ± 0.02 eV; 17 000 ± 150 cm−1). At photon energies of 33 000–41 000 cm−1, exclusively I+ fragments are formed. Over most of this region, the formation of I+ is not energetically allowed via one-photon absorption from the ground state of MgI+. Images show the observed product is due to resonance enhanced two-photon dissociation. The photodissociation spectrum from 33 000 to 38 500 cm−1 shows vibrational structure, giving an average excited state vibrational spacing of 227 cm−1. This is consistent with absorption to the (3) Ω = 0+ state from ν = 0, 1 of the (1) Ω = 0+ ground state; from the (3) Ω = 0+ state, absorption of a second photon results in dissociation to Mg* (3P°J) + I+ (3PJ). From 38 500 to 41 000 cm−1, the spectrum is broad and unstructured. We attribute this region of the spectrum to one-photon dissociation of vibrationally hot MgI+ at low energy and ground state MgI+ at higher energy to form Mg (1S) + I+ (3PJ) products.

Chemistry↗
DOE OSTI2022

Static and dynamic magnetic properties of the spiin-$\frac{5}{2}$triangle lattice antiferromagnet Na 3 Fe(PO 4 ) 2 studied by 31 P NMR

We report 31 P nuclear magnetic resonance (NMR) measurements have been carried out to investigate the magnetic properties and spin dynamics of Fe 3+ (S = 5/2) spins in the two-dimensional triangular lattice (TL) compound Na 3 Fe(PO 4 ) 2 . The temperature (T) dependence of nuclear spin-lattice relaxation rates (1/T 1 ) shows a clear peak around Néel temperature, T N = 10.9 K, corresponding to an antiferromagnetic (AFM) transition. From the temperature dependence of NMR shift (K) above T N , an exchange coupling between Fe 3+ spins was estimated to be J/k B ≃ 1.9 K using the spin-5/2 Heisenberg isotropic-TL model. The temperature dependence of 1/T 1 T divided by the magnetic susceptibility (χ), 1/T 1 T χ , above T N proves the AFM nature of spin fluctuations below ~50 K in the paramagnetic state. In the magnetically ordered state below T N , the characteristic rectangular shape of the NMR spectra is observed, indicative of a commensurate AFM state in its ground state. The strong temperature dependence of 1/T 1 in the AFM state is well explained by the two-magnon (Raman) process of the spin waves in a 3D antiferromagnet with a spin-anisotropy energy gap of 5.7 K. The temperature dependence of sublattice magnetization is also well reproduced by the spin waves. Those results indicate that the magnetically ordered state of Na 3 Fe(PO 4 ) 2 is a conventional 3D AFM state, and no obvious spin frustration effects were detected in its ground state

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Quantum simulation of excited states from parallel contracted quantum eigensolvers

Abstract Computing excited-state properties of molecules and solids is considered one of the most important near-term applications of quantum computers. While many of the current excited-state quantum algorithms differ in circuit architecture, specific exploitation of quantum advantage, or result quality, one common feature is their rooting in the Schrödinger equation. However, through contracting (or projecting) the eigenvalue equation, more efficient strategies can be designed for near-term quantum devices. Here we demonstrate that when combined with the Rayleigh–Ritz variational principle for mixed quantum states, the ground-state contracted quantum eigensolver (CQE) can be generalized to compute any number of quantum eigenstates simultaneously. We introduce two excited-state (anti-Hermitian) CQEs that perform the excited-state calculation while inheriting many of the remarkable features of the original ground-state version of the algorithm, such as its scalability. To showcase our approach, we study several model and chemical Hamiltonians and investigate the performance of different implementations.

Physics↗
DOE OSTI2023

Direct Mass Measurements to Inform the Behavior of 128m $\mathrm{Sb}$ in Nucleosynthetic Environments

Nuclear isomer effects are pivotal in understanding nuclear astrophysics, particularly in the rapid neutron-capture process where the population of metastable isomers can alter the radioactive decay paths of nuclei produced during astrophysical events. The β-decaying isomer 128m Sb was identified as potentially impactful since the β-decay pathway along the A = 128 isobar funnels into this state bypassing the ground state. Here we report the first direct mass measurements of the 128 Sb isomer and ground state using the Canadian Penning Trap mass spectrometer at Argonne National Laboratory. We find mass excesses of -84564.8(25) keV and -84608.8(21) keV, respectively, resulting in an excitation energy for the isomer of 43.9(33) keV. These results provide the first key nuclear data input for understanding the role of 128m Sb in nucleosynthesis, and we show that it will influence the flow of the rapid neutron-capture process.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Evidence for valence-bond pairing in a one-dimensional two-orbital system

Valence bond (VB) states as the formation mechanism of Cooper pairs, eventually leading to high-temperature superconductivity, remain a controversial topic. Although various VB-like states find variational relevance in the description of specific spin models and quantum spin liquids, in the realm of many-body fermionic Hamiltonians, the evidence for such states as ground-state wave functions remains elusive, challenging the valence-bond pairing mechanism. Here, we present evidence of a VB ground state with pairing tendencies, particularly at finite doping. Here, we achieved this for the generic two-orbital Hubbard model in low dimension, where the VB states can be associated with the presence of the topological order manifested by edge states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
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 OSTI2022

Magnetic field effects on the quantum spin liquid behaviors of NaYbS 2

Spin-orbit coupling is an important ingredient to regulate the many-body physics, especially for many spin liquid candidate materials such as rare-earth magnets and Kitaev materials. The rare-earth chalcogenides NaYbCh 2 (Ch = O, S, Se) is a congenital frustrating system to exhibit the intrinsic landmark of spin liquid by eliminating both the site disorders between Na + and Yb 3+ ions with the big ionic size difference and the Dzyaloshinskii-Moriya interaction with the perfect triangular lattice of the Yb 3+ ions. The temperature versus magnetic-field phase diagram is established by the magnetization, specific heat, and neutron-scattering measurements. Notably, the neutron diffraction spectra and the magnetization curve might provide microscopic evidence for a series of spin configuration for in-plane fields, which include the disordered spin liquid state, 120° antiferromagnet, and one-half magnetization state. Furthermore, the ground state is suggested to be a gapless spin liquid from inelastic neutron scattering, and the magnetic field adjusts the spin orbit coupling. Therefore, the strong spin-orbit coupling in the frustrated quantum magnet substantially enriches low-energy spin physics. This rare-earth family could offer a good platform for exploring the quantum spin liquid ground state and quantum magnetic transitions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Transient resonant Auger–Meitner spectra of photoexcited thymine

In this paper, we present the first investigation of excited state dynamics by resonant Auger–Meitner spectroscopy (also known as resonant Auger spectroscopy) using the nucleobase thymine as an example. Thymine is photoexcited in the UV and probed with X-ray photon energies at and below the oxygen K-edge. After initial photoexcitation to a ππ* excited state, thymine is known to undergo internal conversion to an nπ* excited state with a strong resonance at the oxygen K-edge, red-shifted from the ground state π* resonances of thymine. We resolve and compare the Auger–Meitner electron spectra associated both with the excited state and ground state resonances, and distinguish participator and spectator decay contributions. Furthermore, we observe simultaneously with the decay of the nπ* state signatures the appearance of additional resonant Auger–Meitner contributions at photon energies between the nπ* state and the ground state resonances. We assign these contributions to population transfer from the nπ* state to a ππ* triplet state via intersystem crossing on the picosecond timescale based on simulations of the X-ray absorption spectra in the vibrationally hot triplet state. Moreover, we identify signatures from the initially excited ππ* singlet state which we have not observed in our previous study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗