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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 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with the Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas Phase and Solvents Ranging from Hexanes to Acetonitrile

Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). We analyze the performance of polarizable continuum solvation models available in Q-Chem that partition the solvent response into fast and slow time scales, and clear trends emerge when measurements corresponding to the four small 4-(dimethylamino)benzonitrile (DMABN)-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the well-separated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by the linear-response time-dependent density functional theory within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.

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

Adaptive Variational Quantum Computing Approaches for Green’s Functions and Nonlinear Susceptibilities

Here, we present and benchmark quantum computing approaches for calculating real-time single-particle Green’s functions and nonlinear susceptibilities of Hamiltonian systems. The approaches leverage adaptive variational quantum algorithms for state preparation and propagation. Using automatically generated compact circuits, the dynamical evolution is performed over sufficiently long times to achieve adequate frequency resolution of the response functions. We showcase accurate Green’s function calculations using a statevector simulator on classical hardware for Fermi-Hubbard chains of 4 and 6 sites, with maximal ansatz circuit depths of 65 and 424 layers, respectively, and for the molecule LiH with a maximal ansatz circuit depth of 81 layers. Additionally, we consider an antiferromagnetic quantum spin-1 model that incorporates the Dzyaloshinskii-Moriya interaction to illustrate calculations of the third-order nonlinear susceptibilities, which can be measured in two-dimensional coherent spectroscopy experiments. These results demonstrate that real-time approaches using adaptive parametrized circuits to evaluate linear and nonlinear response functions can be feasible with near-term quantum processors.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

The Reliability of Hybrid Functionals for Accurate Fundamental and Optical Gap Prediction of Bulk Solids and Surfaces

Hybrid functionals have been considered insufficiently reliable for the prediction of band gaps in solids and surfaces. We revisit this issue with a new generation of optimally tuned range-separated hybrid functionals, focusing on the reconstructed Si(111)-(2×1) and Ge(111)-(2×1) surfaces. We show that certain hybrid functionals can accurately predict the surface-state and bulk fundamental and optical gaps, as well as projected band structures of these surfaces, by combining ground-state and time-dependent density functional theory.

Sagredo, Francisca↗
DOE OSTI2025

Excited-State Densities from Time-Dependent Density Functional Response Theory

While the variational principle for excited-state energies leads to a route to obtaining excited-state densities from time-dependent density functional theory, relatively little attention has been paid to the quality of the resulting densities in real space obtained with different exchange-correlation functional approximations or how nonadiabatic approximations developed for energies of states of double-excitation character perform for their densities. Here we derive an expression directly in real space for the excited-state density, which includes the case of nonadiabatic kernels and consequently is able, for the first time, to yield densities of states of double-excitation character. Under some well-defined simplifications, we compare the performance of the local-density approximation and exact-exchange approximation, which are in a sense at the opposite extremes of the fundamental functional approximations, on local and charge-transfer excitations in one-dimensional model systems and show that the dressed Time-Dependent Density Functional Theory (TDDFT) approach gives good densities of double excitations.

approximation↗
DOE OSTI2025

Data-Driven Recommendation of Optimal Tuning Scheme for Range-Separated Hybrid Functionals in Solution-Phase UV/Vis Absorption Energy Prediction

Time-dependent density functional theory (TDDFT) combined with range-separated hybrid (RSH) functionals and a tuned range-separation parameter γ offers a computationally economical approach for high-throughput excited- state property predictions. The γ-tuning procedure in the gas phase is well established. However, no agreement on the best γ- tuning procedure has been made when considering the solvent effect with implicit solvent models like the polarizable continuum model (PCM). To answer that question, this study created a diverse dataset with 937 molecules with experimental solutionphase UV/vis absorption spectra. Three γ-tuning methods, the gasphase γ-tuning (GPγT), the partial vertical γ-tuning (PVγT), and the strict vertical γ-tuning (SVγT), were evaluated for the ωPBEh functional over the entire dataset. Additional benchmarks are done for the optimally tuned screened range-separated hybrid combined with the PCM approach (SRSH-PCM) and the solvation-mediated tuning procedure (sol-med-OT). Our findings revealed that the optimal γ-values obtained by the PVγT and the SVγT are significantly smaller than the GPγT. This trend holds consistently across all molecules in our dataset, and we explained the origin of this phenomenon. TDDFT calculations with PVγTand SVγT-tuned γ-values and default global Fock exchange fraction achieve superior performance compared to those using GPγTtuned or default γ and slightly outperform SRSH-PCM and sol-med-OT with similar or lesser computational cost. Furthermore, we found that the smaller γ-values from SVγT captured the expected 1/(εR) asymptotic behavior in the solution phase, resulting in accurate prediction of solution-phase CT excitations, consistent with the screened asymptote behavior encoded in SRSH-PCM. These results show that SVγT is the best scheme for high-throughput UV/vis absorption spectrum calculations using the ωPBEh functional from a data-driven perspective.

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

Computation of Auger Electron Spectra in Organic Molecules with Multiconfiguration Pair-Density Functional Theory

Efficient and accurate computation of molecular Auger electron spectra for larger systems is limited by the rapid increase in the number of doubly ionized final states as the system size grows. Here, in this work, we benchmark the application of multiconfiguration pair-density functional theory with a restricted active space (RAS) reference wave function for computing the carbon K-edge decay spectra of 20 organic molecules. Decay rates are computed within the one-center approximation. We evaluate the performance of different basis sets and on-top functionals and find that multiconfiguration pair-density functional theory achieves accuracy comparable to RAS followed by second-order perturbation theory, but at significantly lower computational cost.

Fouda, Adam E. A. [Argonne National Laboratory (AN↗
DOE OSTI2021

First-Principles Study on the Electronic Properties of PDPP-Based Conjugated Polymer via Density Functional Theory

In this study, we focus on computational predictions of the electronic and optical properties of a one-dimensional periodic model of a single chain of a diketopyrrolopyrrole (DPP)-based conjugated polymer (PDPP3T) as a function of electronic configuration changes due to charge injection. Here, we employ density functional theory (DFT) to explore the ground-state and excited-state electronic properties as well as optical properties influenced by charge injection. We utilize both the Heyd–Scuseria–Ernzerhof (HSE06) and Perdew–Burke–Ernzerhof (PBE) functionals to predict the band gap and compute the absorption spectrum. Our DFT results point out that utilizing the HSE06 functional in conjunction with momentum sampling over the Brillouin zone can appropriately predict the band gap and absorption spectrum in good agreement with experimental data. Moreover, we explore the influence of charge-carrier injection on the electronic configuration of the PDPP3T polymer. Our results indicate that the injection of charge carriers into the PDPP3T semiconducting polymer model greatly affects the electrical properties and ends in a low band gap and high mobility of charge carriers in PDPP3T polymers, offering the potential to tailor the material electronic performance for organic photovoltaic and optoelectronic device applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Toward Chemical Accuracy for Chemi- and Physisorption with an Efficient Density Functional

Understanding molecular adsorption on surfaces underpins many problems in chemistry and materials science. Accurately and efficiently describing the adsorption has been a challenging task for first-principles methods as the process can involve both short-range chemical bond formations and long-range physical interactions, e.g., van der Waals (vdW) interaction. Density functional theory presents an appealing choice for modeling adsorption reactions, although calculations with many exchange-correlation density functional approximations struggle to accurately describe both chemical and physical molecular adsorptions. Here, we propose an efficient density functional approximation that is accurate for both chemical and physical adsorption by concurrently optimizing its semilocal component and the long-range vdW correction against the prototypical adsorption CO/Pt(111) and Ar 2 binding energy curve. The resulting function opens the door to accurate and efficient modeling of general molecular adsorption.

adsorption↗
DOE OSTI2024

Unconventional Error Cancellation Explains the Success of Hartree–Fock Density Functional Theory for Barrier Heights

Energy barriers, which control the rates of chemical reactions, are seriously underestimated by computationally efficient semilocal approximations for the exchange-correlation energy. The accuracy of a semilocal density functional approximation is strongly boosted for reaction barrier heights by evaluating that approximation non-self-consistently on Hartree–Fock electron densities, which has been known for ~30 years. Here, the conventional explanation is that the Hartree–Fock theory yields the more accurate density. This work presents a benchmark Kohn–Sham inversion of accurate coupled-cluster densities for the reaction H 2 + F → HHF → H + HF and finds a strong, understandable cancellation between positive (excessively overcorrected) density-driven and large negative functional-driven errors (expected from stretched radical bonds in the transition state) within this Hartree–Fock density functional theory. This confirms earlier conclusions (Kaplan, A. D., et al. J. Chem. Theory Comput. 2023, 19, 532–543) based on 76 barrier heights and three less reliable, but less expensive, fully nonlocal density functional proxies for the exact density.

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

Elastic Single-Ion Conducting Polymer Electrolytes: Toward a Versatile Approach for Intrinsically Stretchable Functional Polymers

Fabrication of stretchable functional polymeric materials usually relies on the physical adhesion between functional components and elastic polymers, while the interfacial resistance is a potential problem. Herein, a versatile approach on the molecular-level intrinsically stretchable polymer materials with defined functionality is reported. The single-ion conducting polymer electrolytes (SICPEs) were employed to demonstrate the proposed concept along with its potential application in stretchable batteries/electronics with improved energy efficiency and prolonged cell lifetime. The obtained membranes exhibit 88–252% elongation before breaking, and the mechanical properties are well adjustable. The galvanostatic test of the assembled cells using the obtained SICPE membrane exhibited a good cycling performance with a capacity retention of 81.5% after 100 cycles. The applicability of a proposed molecular-level design for intrinsically stretchable polymer materials is further demonstrated in other types of stretchable functional materials, including poly(vinylcarbazole)-based semiconducting polymers and poly(ethylene glycol)-based gas separation membranes.

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

Controlling the Structure of MoS 2 Membranes via Covalent Functionalization with Molecular Spacers

Restacked two-dimensional (2D) materials represent a new class of membranes for water-ion separations. Understanding the interplay between the 2D membrane’s structure and the constituent material’s surface chemistry to its ion sieving properties is crucial for further membrane development. In this paper, we reveal, and tune via covalent functionalization, the structure of MoS 2 -based membranes. We find features on both the ~1 nm (interlayer spacing) and ~100 nm (mesoporous voids between layers) length scales that evolve with the hydration level. The functional groups act as permanent molecular spacers, preventing local impermeability caused by irreversible restacking and promoting the uniform rehydration of the membrane. Molecular dynamics simulations show that the choice of functional group tunes the structure of water within the MoS 2 channel and consequently determines the hydrated interlayer spacing. We demonstrate that MoS 2 membranes functionalized with acetic acid have consistently ~92% rejection of Na 2 SO 4 with a flux of ~1.5 lm -2 hr -1 bar -1 .

2D channel↗
DOE OSTI2020

Biomimetic Rebuilding of Multifunctional Red Blood Cells: Modular Design Using Functional Components

The design and synthesis of artificial materials that mimic the structures, mechanical properties, and ultimately functionalities of biological cells remains a current holy grail of materials science. Here based on a silica cell bio-replication approach, we report the design and construction of synthetic rebuilt red blood cells (RRBCs) that fully mimic the broad properties of native RBCs: size, biconcave shape, deformability, oxygen carrying capacity, long circulation time. Four successive nano-scale processing steps: RBC bioreplication, layer-by-layer polymer deposition, and precision silica etching, followed by RBC ghost membrane vesicles fusion are employed for RRBC construction. A panel of physicochemical analyses including zeta potential measurement, fluorescence microscopy, and antibody-mediated agglutination assay proved the recapitulation of RBC shape, size, and membrane structure. Flow-based deformation studies carried out in a microfluidic blood capillary model confirrned the ability of RRBCs to deform and pass through small slits and reconstitute themselves in a manner comparable to native RBCs. Circulation studies of RRBCs conducted ex-ovo in a chick embryo and in vivo in a mouse model demonstrated the requirement of both deformability and native cell membrane surface to achieve long-term circulation. To confer additional non-native functionalities to RRBCs, we developed modular procedures in which to load functional cargos such as hemoglobin, drugs, magnetic nanoparticles, and ATP biosensors within the RRBC interior to enable various functions, including oxygen delivery, therapeutic drug delivery, magnetic manipulation, and toxin biosensing and detection. Taken together, RRBCs represent a class of long circulating RBC-inspired artificial hybrid materials with a broad range of potential applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Modeling Multi-Step Organic Reactions: Can Density Functional Theory Deliver Misleading Chemistry?

Many organic reactions are characterized by a complex mechanism with a variety of transition states and intermediates of different chemical natures. Their correct and accurate theoretical characterization critically depends on the accuracy of the computational method used. In this work, we study a complex ambimodal cycloaddition with five transition states, two intermediates, and three products, and we ask whether density functional theory (DFT) can provide a correct description of this type of complex and multifaceted reaction. Our work fills a gap in that most systematic benchmarks of DFT for chemical reactions have considered much simpler reactions. Our results show that many density functionals not only lead to seriously large errors but also differ from one another in predicting whether the reaction is ambimodal. Only a few of the available functionals provide a balanced description of the complex and multifaceted reactions. The parameters varied in the tested functionals are the ingredients, the treatment of medium-range and nonlocal correlation energy, and the inclusion of Hartree–Fock exchange. Furthermore, these results show a clear need for more benchmarks on the mechanisms of large molecules in complex reactions.

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

Tetracene Functionalized Si(111) Achieves Enhanced Solar-to-Chemical Energy Conversion via Molecular Acceptor States

The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO 2 surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements. Surface photovoltage (SPV) spectroscopy shows that surfaces modified with Anth or Tet exhibit an increased photovoltage, with Tet-functionalized surfaces yielding an additional 192 meV relative to methyl-terminated Si(111), indicating improved charge separation for Si-Tet. Further improvement in onset potential was achieved by replacing a nitrogen-containing TiO 2 atomic layer deposition (ALD) precursor (TDMAT) with a precursor lacking nitrogen (TTIP), which eliminates the parasitic defect band in the TiO 2 overlayer (p-Si(111)-Tet|TTIP-TiO 2 |Pt: V OC = +0.283 ± 0.041 V vs RHE). Density functional theory (DFT) analysis demonstrates that compared with Anth-modified Si(111), the Tet-modified surface exhibits more hybridized Si(111)-Tet states closer to the silicon band edges. Mercury contact current–voltage (I–V, dark) measurements quantified the relative interfacial density of states of Si-Tet, Si-Anth and Si-Me surfaces─revealing that the interfacial state density was highest for Si-Tet. This suggests that such hybridized interfaces serve to capture better photoexcited charge, which enables facile electron transfer to molecular acceptors in solution. Altogether, the data indicate that beneficial hybrid molecular LUMO surface states interacting with the Si conduction band edge results in improved hydrogen evolution (HER) performance for p-Si devices.

Group theory↗
DOE OSTI2022

A functional map of HIV-host interactions in primary human T cells

Human Immunodeficiency Virus (HIV) relies on host molecular machinery for replication. Systematic attempts to genetically or biochemically define these host factors have yielded hundreds of candidates, but few have been functionally validated in primary cells. Here, we target 426 genes previously implicated in the HIV lifecycle through protein interaction studies for CRISPR-Cas9-mediated knock-out in primary human CD4+ T cells in order to systematically assess their functional roles in HIV replication. We achieve efficient knockout (>50% of alleles) in 364 of the targeted genes and identify 86 candidate host factors that alter HIV infection. 47 of these factors validate by multiplex gene editing in independent donors, including 23 factors with restrictive activity. Both gene editing efficiencies and HIV-1 phenotypes are highly concordant among independent donors. Importantly, over half of these factors have not been previously described to play a functional role in HIV replication, providing numerous novel avenues for understanding HIV biology. These data further suggest that host-pathogen protein-protein interaction datasets offer an enriched source of candidates for functional host factor discovery and provide an improved understanding of the mechanics of HIV replication in primary T cells.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Dynamic conformational switching underlies TFIIH function in transcription and DNA repair and impacts genetic diseases

Transcription factor IIH (TFIIH) is a protein assembly essential for transcription initiation and nucleotide excision repair (NER). Yet, understanding of the conformational switching underpinning these diverse TFIIH functions remains fragmentary. TFIIH mechanisms critically depend on two translocase subunits, XPB and XPD. To unravel their functions and regulation, we build cryo-EM based TFIIH models in transcription- and NER-competent states. Using simulations and graph-theoretical analysis methods, we reveal TFIIH’s global motions, define TFIIH partitioning into dynamic communities and show how TFIIH reshapes itself and self-regulates depending on functional context. Our study uncovers an internal regulatory mechanism that switches XPB and XPD activities making them mutually exclusive between NER and transcription initiation. By sequentially coordinating the XPB and XPD DNA-unwinding activities, the switch ensures precise DNA incision in NER. Mapping TFIIH disease mutations onto network models reveals clustering into distinct mechanistic classes, affecting translocase functions, protein interactions and interface dynamics.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

A linear response framework for quantum simulation of bosonic and fermionic correlation functions

Response functions are a fundamental aspect of physics; they represent the link between experimental observations and the underlying quantum many-body state. However, this link is often under-appreciated, as the Lehmann formalism for obtaining response functions in linear response has no direct link to experiment. Within the context of quantum computing, and via a linear response framework, we restore this link by making the experiment an inextricable part of the quantum simulation. This method can be frequency- and momentum-selective, avoids limitations on operators that can be directly measured, and can be more efficient than competing methods. As prototypical examples of response functions, we demonstrate that both bosonic and fermionic Green’s functions can be obtained, and apply these ideas to the study of a charge-density-wave material on the ibm_auckland superconducting quantum computer. The linear response method provides a robust framework for using quantum computers to study systems in physics and chemistry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Simultaneous enhancement of multiple functional properties using evolution-informed protein design

Abstract A major challenge in protein design is to augment existing functional proteins with multiple property enhancements. Altering several properties likely necessitates numerous primary sequence changes, and novel methods are needed to accurately predict combinations of mutations that maintain or enhance function. Models of sequence co-variation (e.g., EVcouplings), which leverage extensive information about various protein properties and activities from homologous protein sequences, have proven effective for many applications including structure determination and mutation effect prediction. We apply EVcouplings to computationally design variants of the model protein TEM-1 β -lactamase. Nearly all the 14 experimentally characterized designs were functional, including one with 84 mutations from the nearest natural homolog. The designs also had large increases in thermostability, increased activity on multiple substrates, and nearly identical structure to the wild type enzyme. This study highlights the efficacy of evolutionary models in guiding large sequence alterations to generate functional diversity for protein design applications.

59 BASIC BIOLOGICAL SCIENCES↗