Search NASA⌕ Search

SEARCH · Search NASA

Results for “time-dependent density functional theory”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Structural Evidence of Interanionic Hydrogen Bonding in Phosphoric Acid Solutions

Interanionic hydrogen bonding (IAHB) is a noncovalent interaction between like-charged ions that challenges conventional electrostatic understanding. This study provides direct structural evidence of IAHB in concentrated aqueous phosphoric acid (PA) solutions, which exhibit >60% dissociation under these conditions. Oxygen K-edge X-ray absorption fine structure spectroscopy, combined with electron affinity time-dependent density functional theory calculations, reveals the formation of stable, cyclic phosphate-phosphate IAHB dimers at PA concentrations ≥7 M. Extended X-ray absorption fine structure data show distinct long-range ordering consistent with these dimers, and near-edge X-ray absorption fine structure spectra confirm a concentration-dependent transition from monomeric to dimeric species. Energy decomposition analysis through density functional theory shows that the formation of solution-phase IAHB is energetically favored and is attributed to polarization of and the charge transfer between the two fragments driven by the surrounding solvent molecules, in addition to the permanent electrostatics. These findings offers crucial structural insights into the H-bonded networks in concentrated PA, highlighting the critical role of solvent in facilitating anion–anion association.

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

Helical Complex Ladder Polymer with Amplification of Asymmetry

Here, we report a Cu–salen helical complex ladder polymer (HLP-Cu) built from covalently fused Cu(Salen) units. Point chirality from enantiopure diamines directs the formation of a rigid, π-conjugated helix. Compared with a planar analogue (LLP-Cu) and the Cu(Salen) monomer, HLP-Cu exhibits up to 5-fold stronger circular dichroism and a maximum dissymmetry factor of 7.4 × 10 –3 . Titration experiments suggest a cooperative amplification of asymmetry arising from extended conjugation and helical geometry during helix formation. Time-dependent density functional theory calculations are employed to support this hypothesis, showing that increasing conjugation length and helical order enhance the rotational strength of contributing excited states via elevated magnetic transition moments and improved alignment of electric and magnetic transition moments. Our findings provide a new polymer platform for designing functional chiral materials with tunable chiroptical and spin-dependent properties.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Quantum effects on the dynamics and properties of soft materials

The quantum effects of nuclear and electronic motion play an important role in the structure, dynamics, and function of soft materials, yet they are difficult to capture with conventional classical simulations or static electronic–structure methods. In this work several complementary approaches for treating quantum effects in polymeric and soft–matter systems are demonstrated, with a focus being on the hydrogen-bonded networks, ion and charge transport, and photoactive chromophores. The proton transfer, tunneling, and isotope effects are captured within the reduced-dimensionality models by implementing grid-based nuclear quantum dynamics in terms of the discrete variable and Fourier bases. The nuclear quantum dynamics is extended to larger systems by employing the quantum trajectories and quantum–thermal bath schemes combined with on-the-fly electronic structure, enabling the description of high-dimensional polymeric environments at feasible cost. The dynamics in the electronic degrees of freedom, simulating the optical response in large chromophores such as chlorophylls, is performed using the real-time time-dependent density functional theory implemented in the real-space multigrid (RMG) code. These approaches are demonstrated on case studies of the proton and hydroxide transport in hydrated polymer membranes, charge transfer in conjugated polymers, and the optical spectra of chlorophyll chromophores relevant to polymerized chlorophyll materials and chlorophyll–polymer hybrids. The reviewed methods and applications highlight practical routes of including quantum effects in simulations of soft functional materials.

Garashchuk, Sophya [Univ. of South Carolina, Colum↗
DOE OSTI2025

Photoinduced electronic excitations drive polymerization of carbon monoxide: A first-principles study

Under pressure, carbon monoxide (CO) transforms into a polymer that can be recovered to ambient conditions. While this transformation can occur without additional stimuli, experimental observations have shown that laser irradiation can induce a similar transformation at reduced pressure. The resulting polymeric phase, which is metastable under ambient conditions, releases energy through decomposition into more stable configurations. Using time-dependent density functional theory and Born–Oppenheimer molecular dynamics simulations, we investigate the mechanism by which electronic excitation facilitates CO polymerization. Our calculations reveal that electronic excitation enhances carbon–carbon bonding, enabling polymerization at pressures significantly lower than those required by conventional compression methods. In conclusion, these findings suggest that a photo-assisted approach could be employed to synthesize novel, potentially energetic materials under less demanding pressure conditions.

Born-Oppenheimer molecular dynamics↗
DOE OSTI2025

Nonadiabatic dynamics of photoexcited thiopyridone isomers: An interplay between El-Sayed’s conditions and energy gap law

We investigated the non-adiabatic dynamics of photoexcited thiopyridone systems across their ortho-, meta-, and para-isomeric forms. The relaxation pathways of the three isomers in both gas phase and solvent environments are mapped using surface hopping dynamics based on time-dependent density functional theory. Our analysis highlights the influence of isomeric structures on photophysical behavior, offering insights into design principles to control photochemical phenomena. The simulations suggest a systematic reduction in the rate of intersystem crossing (ISC) from ortho- to meta- to para-isomer. Comparisons with multiconfigurational wave function methods in the gas phase further demonstrate how electronic structure influences the predicted dynamical pathways. The simulated dynamics demonstrates that the spin–orbit coupling strength alone does not determine the rate of ISC, as both state energetics and underlying electronic and structural features play decisive roles. These aspects explain the much slower ISC in the para-isomer, as well as the non-negligible role of the El-Sayed forbidden pathway in the computed ISC dynamics.

Complete-active space self-consistent field↗
DOE OSTI2025

Perspective on Many-Body Methods for Molecular Polaritonic Systems

Recent advances in strong light–matter interactions have revealed a wealth of new physical phenomena in molecules embedded in optical cavities, including modified chemical reactivity, altered excitation spectra, and novel quantum correlations. To describe these effects from first-principles, the field of ab initio quantum electrodynamics (QED) has emerged as a compelling extension of quantum chemistry that treats electronic and photonic degrees of freedom on equal footing. In this Perspective, we review the growing landscape of many-body QED methods, including Hartree–Fock, density functional theory (QEDFT), time-dependent DFT (QED-TDDFT), configuration interaction (QED-CI), complete active space (QED-CASSCF), coupled cluster (QED-CC), quantum Monte Carlo (QED-QMC), and density matrix renormalization group (QED-DMRG), highlighting recent developments and implementations. We further explore real-time methods, gradient and Hessian formalisms, and the integration of nonadiabatic nuclear dynamics. Applications range from benchmark simulations of polaritonic chemistry to quantum simulations on emerging quantum hardware. We conclude by outlining future directions for theory development and interdisciplinary efforts at the interface of quantum chemistry, condensed matter, and quantum optics.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Dynamics of ballistic photocurrents driven by Coulomb scattering in a two-dimensional material

First-principles real-time time-dependent density-functional theory (rt-TDDFT) calculations reveal the existence of ballistic photocurrents generated by Coulomb scattering, which has not previously been considered as a mechanism for the bulk photovoltaic effect. With monolayer GeS as an example, it is predicted that ballistic currents can be comparable to shift currents under experimentally accessible conditions.

2-dimensional systems↗
DOE OSTI2025

Zinc(II) Monomeric, Dimeric, and Trimeric Photosensitizers with Microsecond‐Lived Intra‐ligand Charge Transfer Excited States Investigated through Time‐Resolved Optical and X‐Ray Spectroscopy

Zn II photosensitizers relative to Cu I complexes have received less attention due to their energetically higher metal‐to‐ligand charge transfer states. Three Zn II complexes, namely a Monomer, a bimetallic helicate, and a trimetallic helicate, bearing phenanthroline ligands are hereby studied through time‐resolved X‐ray absorption (tr‐XAS) and femto‐microsecond optical transient absorption spectroscopy (OTA). The formation of intraligand singlet charge transfer ( I ILCT) excited states is achieved within femtoseconds, followed by intersystem crossing (ISC) in nanoseconds to generate microsecond‐lived triplet ( 3 ILCT) states. Femtosecond OTA shows that the 1 ILCT states in the Monomer, Dimer, and Trimer occur within 235 fs, 683 fs, and 730 fs, respectively, while nano‐microsecond OTA and tr‐XAS show their 3 ILCT states to decay within 1.00 µs, 1.48 µs, and 1.51 µs. The ISC from the 1 ILCT to the 3 ILCT state for the Trimer is 42.8 ns compared to the Monomer and Dimer with ISC rates of less than 13 ns. These differences arise due to the stabilization by π‐π and CH‐π noncovalent interactions of the phenanthroline ligands. The dihedral and torsional angles indicate stronger ligand strains in the excited states of the Dimer and Trimer versus the Monomer. DFT calculations for the electrochemical oxidation potentials further highlight their capability in inducing photoredox processes.

earth-abundant Zn-based photosensitizers↗
DOE OSTI2025

Density Functional Tight Binding Insights into Plasmonic Silver–Platinum Nanoparticles and Alloys for Enhanced Photocatalysis

Developing accurate and efficient Slater-Koster (SK) tight-binding parameter sets is essential for quantum plasmonic studies of alloyed metal nanoparticles, as conventional time dependent density functional theory (TD-DFT) calculations are computationally prohibitive for larger clusters. In this work, we develop and validate density functional tight binding (DFTB) parameter sets for both ground state (GS-SK) and excited state (ES-SK) calculations to study the structural, electronic, and optical properties of silver (Ag), platinum (Pt), and Ag–Pt nanoalloys. Our investigation of the ground state properties demonstrates that the GS-SK parameters enable DFTB to closely reproduce the electronic structures of platinum clusters with diverse sizes and geometries – showing qualitative agreement with DFT for density of states (DOS) profiles and energy levels. The ES-SK parameters accurately describe excited-state properties compared to TD-DFT reference calculations, including the broad, featureless absorption profiles of Pt that are dominated by interband transitions. Using the ES-SK parameters within a real-time TD-DFTB framework, we compute size-dependent optical absorption spectra of Ag, Pt and Ag-Pt nanocubes containing up to 1099 atoms (size ∼4.18 nm). A detailed study of Ag–Pt and Pt-Ag core–shell nanoparticles shows quenching of the Ag plasmon resonance even at monolayer coverage for Ag-Pt, but not for Pt-Ag. We also show how to define submonolayer Ag-core Pt-shell cubic structures that have similar optical properties to those generated experimentally for much larger particles, which offers potential for describing plasmon-enhanced photocatalysis. Collectively, the GS-SK and ES-SK parameter sets provide an accurate, computationally efficient approach for modeling the complex optical and electronic behavior of noble–transition metal nanostructures and their alloys.

SPR↗
DOE OSTI2026

When Do Band Gap Calculations Agree with Experiments in Monolayer-Protected Cu 14 and Au 20 Atomically Precise Nanoclusters? A (TD)-DFT Comparison of HOMO–LUMO, Fundamental, Optical, and Electrochemical Energy Gaps

In view of the tremendous progress in atomically precise metal nanoclusters where electrochemical and optical energetics are routinely supported by computations to establish structure−function correlations, we explore the relationship between different protocols for measuring and computing band gaps of two distinct organic ligand-protected nanoclusters: [Cu 14 H 10 (MBN) 3 (PPh 3 ) 8 ] + and Au 20 (TBBT) 16 . Through UV/visible spectroscopy and differential pulse voltammetry, we measure optical and electrochemical band gaps in those systems. We then compare these experimentally determined gaps to HOMO−LUMO gaps, fundamental gaps, vertical excitation energies, and E o ox − E o red potentials computed using different density functional theory (DFT) or time-dependent DFT (TDDFT) methods. Specifically, in both copper and gold nanoclusters, we test the effect of truncating inert ligands from the model and compare density functionals with varying degrees of Hartree−Fock (HF) exchange from 0 to 50%, range-separated hybrids with a varying long-range tuning parameter, different correlation functionals, basis sets, and (equilibrium and nonequilibrium) continuum solvation models. Despite having different frontier orbital characters (the copper nanocluster has a metal-to-ligand charge transfer character while the gold nanocluster has metal-centered frontier orbitals), both nanoclusters display a similar sensitivity of the HOMO−LUMO gap to the HF exchange that is partially mitigated when computing the fundamental, optical, and electrochemical gaps. Other factors, such as the nature of the correlation functional, basis set, and geometry relaxation, have a considerably smaller effect on computed band gaps in these systems. Overall, this work provides guidelines for factors of varied importance for correlating computed and experimental band gap values.

Chemical calculations↗
DOE OSTI2026

Exploring the Origins of Anti-Ambipolarity in BBL Polymer: Links to Redox Chemistry, Electronic Structure, and Structural Dynamics

We examine the intrinsic physical-chemical properties of the conjugated ladder-type polymer poly(benzimidazobenzophenanthroline) (BBL) in response to electron transfer. We aim at explaining the origin of the anti-ambipolar behavior behind the observed BBL nonlinear response associated with specific device architectures. To elucidate this point, we use theory and computation based on first principles, including density functional theory optimizations, ab initio molecular dynamics, time-dependent DFT, and Marcus-theory analysis. Our results reveal that this redox response is not simply monotonic but follows an alternating odd/even pattern in which gap narrowing and reopening occur sequentially before near-gapless behavior emerges at high charging. Converging theoretical evidence in this work demonstrates that bell shaped conductivity in BBL originates in its fundamental electronic structure and supramolecular organization.

FOS: Physical sciences↗
DOE OSTI2026

High-Yield Room-Temperature Aryl 211 At Radiolabeling via Redox-Activated Column-Shipped 211 At

Efficient late-stage formation of aryl– 211 At bonds is relevant to expanding the scope of targeted α-therapy radiopharmaceuticals. In this work, a catalyst-enabled astatodeboronation approach is evaluated using wet chemically regenerated 211 At recovered from shipped 3-octanone-impregnated columns. A series of aryl boronic esters bearing electron-donating and electron-withdrawing substituents were radiolabeled under mild conditions, with reaction parameters examined through time-dependent studies. Radiochemical conversions ranging from 68–97% were observed across the substrate set. Density functional theory calculations were employed as a qualitative framework to contextualize relative B–C and At–C bonding descriptors. Overall, this study demonstrates that wet chemically regenerated 211 At can be applied to the late-stage labeling of aryl boronic esters under mild conditions and provides guidance for future exploration of 211 At radiolabeling strategies.

211At-aryl labeling↗
DOE OSTI2025

Production of neutron-rich heavy nuclei in deep-inelastic 208 Pb + 208 Pb collisions within the stochastic mean-field theory

In deep-inelastic collisions of heavy nuclei, reaction products with a wide range of mass and charge are produced. Such collisions been considered as a possible way to produce superheavy nuclei, as an alternative to fusion reactions. To provide reliable theoretical predictions, it is desired to develop microscopic approaches that correctly and accurately describe nucleon transfer processes in dissipative collisions of heavy nuclei. The purpose of the present work is (1) to investigate the mechanism of nucleon transfers in dissipative collisions of two heavy nuclei, and (2) to explore possible pathways to produce neutron-rich heavy nuclei, through detailed theoretical analyses of fluctuations and correlations in nucleon transfers in 208 Pb + 208 Pb reactions. Three-dimensional time-dependent Hartree-Fock (TDHF) calculations are performed for the collisions of 208 Pb + 208 Pb at 𝐸 c.m. = 832, 936, and 1040 MeV, using the Skyrme SLy4d energy density functional. To calculate fluctuations and correlations in nucleon transfers, we employ the stochastic mean-field (SMF) theory, and the results are compared with another theoretical framework currently available, the time-dependent random phase approximation (TDRPA). Primary and secondary production cross sections are calculated with the SMF theory combined with a statistical model, GEMINI ++ . Using information of nucleon flow across a neck of colliding nuclei in TDHF calculations, we solve quantal diffusion equations for fluctuations and correlations in nucleon transfers based on the SMF theory. From the SMF calculations, we obtain the time evolution of diffusion coefficients as well as fluctuations and correlations in nucleon transfers for a range of initial orbital angular momenta. We compare the results of the SMF calculations with those of TDRPA, showing that TDRPA tends to predict substantially larger fluctuations and correlations in strongly damped collisions of heavy nuclei, which exhibit complex initial angular momentum dependence, while the SMF results provide almost constant (stable) values. Using the obtained fluctuations and correlations, we calculate primary and secondary production cross sections for the 208 Pb + 208 Pb collisions. From the results, we find that both lighter and heavier reaction products as compared to 208 Pb are produced for a wide region in the 𝑁−𝑍 plane as primary products, thanks to the quantal diffusion mechanism in the dissipative collisions. However, we show that cross sections for production of heavy nuclei with 𝑍 ≳ 90 or 𝑁 ≳ 135 are washed out due to secondary particle evaporation and/or fission processes. On the other hand, we find that there remain sizable cross sections for production of neutron-rich nuclei along 𝑁 = 126 with 𝑍< 82, even after secondary disintegration processes. We demonstrate that the secondary production cross sections depend weakly on incident energies, but lower (higher) energy is slightly preferred for production of nuclei with smaller (larger) atomic numbers as compared to 𝑍 = 82. Here, based on the microscopic SMF calculations, it has been shown that deep-inelastic collisions of heavy nuclei, such as 208 Pb + 208 Pb examined in this study, can be a promising means to produce neutron-rich heavy nuclei along 𝑁=126. Discrepancies between the SMF and TDRPA approaches are left unsolved for future investigations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Computing nuclear response functions with time-dependent coupled-cluster theory

We compute nuclear response functions by solving the time-dependent 𝐴-body Schrödinger equation, recording the time-dependent transition moment and extracting spectral information via Fourier transforms. The solution of the time-dependent many-body problem accounts for correlations on top of the mean field by taking advantage of a time-dependent formulation of coupled-cluster theory. As a validation, we focus on electric dipole transitions in 4 He and 16 O and compare moments of the response function distribution to the results of an equivalent static framework, finding negligible discrepancies. We investigate how proton and neutron densities evolve in time, and we see the traditional picture of soft and giant dipole resonances as collective oscillations of protons and neutrons emerging from our calculations in 16 O and 24 O. Furthermore, this method also allows us to investigate the behavior of the nucleus in the presence of a strong electric field. In that regime, the behavior of the system becomes chaotic. Qualitatively, the spectral information obtained in this limit is in line with previous time-dependent mean-field results.

Ab initio calculations↗
DOE OSTI2025

Beyond Magic Barrels: Digital manufacturing for crystallization, process development and optimization of explosive materials: Part II Resveratrol Exemplar

This SAND report summarizes work supported by an Engineering Sciences Research Foundation (ESRF) Lab Directed Research and Development (LDRD) project entitled “Beyond Magic Barrels: Digital manufacturing for crystallization, process development and optimization of explosive materials.” This SAND report is written in two parts with Part 1 discusses recrystallization of our explosive exemplar and Part 2 summarizing our work with recrystallization of resveratrol. We have studied resveratrol recrystallization with a multiscale approach combining experiments, modeling and simulation. At the single crystal scale, microscopy experiments illuminate crystal time-dependent growth rates using advanced image analysis. Bench scale experiments were carried out to look at growth of multiple particles in a small reactor creating thousands of particles and analyzing the results with microscopy and μCT. For the modeling we combine kinetic Monte Carlo (kMC) models with subscale information from density functional theory (DFT) or molecular dynamics. This work is discussed in Part 1 and can also be found in a paper from the project discussing a coarse-grained kMC model specifically developed for resveratrol. For well-mixed systems, we have population balance equations (PBE) linked with species mass conservation forming a set of ordinary differential equations that can be solved quickly. For more complicated geometries, such as the vat crystallization used throughout the complex, a coupled computational fluid dynamic (CFD)/PBE method was developed to account for gradients in temperature and concentration and differences in crystallization rates throughout the domain. These simulations are more complex and require high performance computing. We present results for two cases: 5% seed fast cool with parameters fit to the well-mixed case and 5% seed slow cool using the same parameters. We show reasonable agreement with experiments though are particles are significantly larger than the experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2025

An Atomistic Study of Reactivity in Solid-State Electrolyte Interphase Formation for Li/Li7P3S11

Lithium metal batteries offer superior volumetric and gravimetric specific capacities compared to those based on traditional graphite anodes. Although advancements in solid-state electrolytes address safety concerns, challenges remain, particularly regarding interphase formation in lithium metal anodes. This work presents a computational framework based on high-throughput first-principles density functional theory and machine-learning interatomic potentials (MLIPs) including automated iterative, active learning to enable robust computational exploration of interphase formation between lithium metal anodes and an inorganic solid-state electrolyte. As a demonstration, we apply the framework to a Li/Li7P3S11 interface and find that it accurately identifies the experimentally observed, thermodynamically stable interphase products as well as their overall spatial arrangement within a heterogeneous, amorphous layered structure, with Li2S domains of nanocrystallinity. Our simulations show two stages, a fast and slow diffusion reaction regime, that corroborate the relative phase formation rate of Li x P, Li2S, and Li3P. Using the Onsager transport theory, we capture time-dependent ionic diffusion within the reacting interface, including cross-correlation effects. We found that cross-correlation effects between Li-P and P-S ionic motion significantly influence P-ion diffusion, making it highly sensitive to the local environment and potentially leading to "kinetic trapping" of Li-P phases. The passivation of the interface is shown as the ionic fluxes all approach zero, effectively halting interphase growth.

Diffusion↗
DOE OSTI2026

Mixed stochastic-deterministic density functional theoretic decomposition of Kubo–Greenwood conductivities in the projector augmented wave formalism

Pairing the accuracy of the Kohn–Sham density-functional framework with the efficiency of a stochastic algorithmic approach, mixed stochastic-deterministic density functional theory (mDFT) achieves a favorable computational scaling with system sizes and electronic temperatures. We employ the recently developed mDFT formalism to investigate the dynamic charge-transport properties of systems in the warm dense matter regime. The optical conductivity spectra are computed for single- and multi- component mixtures of carbon, hydrogen, and beryllium using two complementary approaches: Kubo–Greenwood in the mDFT picture and real-time time-dependent mDFT. We further devise a decomposition of the Onsager coefficients leading up to the Kubo–Greenwood spectra to exhibit contributions from the deterministic, stochastic, and mixed electronic state transitions at different incident photon energies.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Comparison between explicit and implicit discretization strategies for a dissipative thermal environment

We investigate strategies for simulating open quantum systems coupled to dissipative baths by comparing explicit wave function-based discretization [via multi-layer multi-configuration time-dependent Hartree (ML-MCTDH)] and the implicit density matrix-based master equation method [via tree tensor network hierarchical equations of motion (TTN-HEOM)]. For dissipative baths characterized by exponentially decaying bath correlation functions, the implicit discretization approach of HEOM—rooted in bath correlation function decompositions—proves significantly more efficient than explicit discretization of the bath into discrete harmonic modes. Explicit methods, like ML-MCTDH, require extensive mode discretization to approximate continuum baths, leading to computational bottlenecks. Case studies for two-level systems and a Fenna–Matthews–Olson complex model highlight TTN-HEOM’s superiority in capturing dissipative dynamics with relaxations with a minimal number of auxiliary modes, while the explicit methods are as exact as the HEOM in pure dephasing regimes. This comparison is enabled by the TENSO package, which has both ML-MCTDH and TTN-HEOM implemented using the same computational structure and propagation strategy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗