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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Impact of solvation on the electronic resonances in uracil

Interactions of low-energy electrons with the DNA and RNA nucleobases are known to form metastable states, known as electronic resonances. In this work, we study electron attachment to solvated uracil, an RNA nucleobase, using the orbital stabilization method at the Equation of Motion-Coupled Cluster for Electron Affinities with Singles and Doubles (EOM-EA-CCSD) level of theory with the Effective Fragment Potential (EFP) solvation method. We benchmarked the approach using multireference methods, as well as by comparing EFP and full quantum calculations. The impact of solvation on the first one particle (1p) shape resonance, formed by electron attachment to the π* LUMO orbital, as well as the first two particle one hole (2p1h) resonance, formed by electron attachment to neutral uracil's π–π* excited state, was investigated. We used molecular dynamics simulations for solvent configurations and applied charge stabilization technique-based biased sampling to procure configurations adequate to cover the entire range of the electron attachment energy distribution. The electron attachment energy in solution is found to be distributed over a wide range of energies, between 4.6 eV to 6.8 eV for the 2p1h resonance, and between −0.1 eV to 2 eV for the 1p resonance. The solvent effects were similar for the two resonances, indicating that the exact electron density of the state is not as important as the solvent configurations. Multireference calculations extended the findings showing that solvation effects are similar for the lowest four resonances, further indicating that the specific solute electron density is not as important, but rather the water configurations play the most important role in solvation effects. Lastly, by comparing bulk solvation to clusters of uracil with a few water molecules around it, we find that the impact of microsolvation is very different from that of bulk solvation.

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

Photoelectron Spectroscopic and ab Initio Computational Studies of the Anion, HThO –

The synergetic combination of anion photoelectron spectroscopy and high-level relativistic coupled-cluster calculations was employed to study the anion, HThO-. The atomic connectivity of this anion was found to be HThO- and not ThOH-. Vibrational and electronic energy spacings in the HThO- photoelectron spectrum were measured and calculated, with good agreement between them being found. Computations yielded electronic energies and equilibrium structures as well as enabling orbital analyses. The adiabatic electron affinity of HThO was determined to be 1.297 ± 0.035 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Localization Effect in Photoelectron Transport Induced by Alloy Disorder in Nitride Semiconductor Compounds

Near-band-gap photoemission spectroscopy experiments were performed on p-GaN and p-InGaN/GaN photocathodes activated to negative electron affinity. Here, the photoemission quantum yield of the InGaN samples with more than 5% of indium drops by more than 1 order of magnitude when the temperature is decreased while it remains constant for lower indium content. This drop is attributed to a freezing of photoelectron transport in p-InGaN due to electron localization in the fluctuating potential induced by the alloy disorder. This interpretation is supported by the disappearance at low temperature of the peak in the photoemission spectrum that corresponds to the contribution of the photoelectrons relaxed at the bottom of the InGaN conduction band.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Photoelectron spectroscopy of cryogenically cooled NiO 2 – via slow photoelectron velocity-map imaging

In this work, high-resolution anion photoelectron spectra of cryogenically cooled NiO 2 – anions, obtained using slow photoelectron velocity-map imaging (cryo-SEVI), are presented in tandem with coupled cluster electronic structure calculations including relativistic effects. The experimental spectra encompass the $\tilde{\text{X}}^1Σ_{\text{g}}^+ ← \tilde{\text{X}}^2Π_{\text{g}}, ã^3Π{\text{g}} ← \tilde{\text{X}}^2Π_{\text{g}}$, and $\tilde{\text{A}}^1Π_{\text{g}} ← \tilde{\text{X}}^2Π_{\text{g}}$ photodetachment transitions of linear ONiO 0/– , revealing previously unobserved vibrational structure in all three electronic bands. The high-resolution afforded by cryo-SEVI allows for the extraction of vibrational frequencies for each state, consistent with those previously measured in the ground state and in good agreement with scalar-relativistic coupled-cluster calculations. Previously unobserved vibrational structure is observed in the $ã^3Π_{\text{g}}$ and $Ã^1Π_{\text{g}}$ states and is tentatively assigned. Further, a refined electron affinity of 3.0464(7) eV for NiO 2 is obtained as well as precise term energies for the ã and à states of NiO 2 of 0.3982(7) and 0.7422(10) eV, respectively. Numerous Franck–Condon forbidden transitions involving the doubly degenerate $ν_2$ bending mode are observed and ascribed to Herzberg-Teller coupling to an excited electronic state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

The photodetachment cross-section and threshold energy of negative ions in carbon dioxide

Threshold energy and sunlight photodetachment measurements on negative carbon dioxide ions, using a 2.5 kw light pressure xenon lamp, show that: (1) Electron affinity of CO3(+) is larger than 2.7 e.V. and that an isomeric form of CO3(+) is likely an error; (2) The photodetachment cross section of CO3(-) will roughly be like a step function across the range of 4250 to 2500A, having its threshold energy at 4250A; (3) Sunlight photodetachment rate for CO3(-) is probably much smaller than elsewhere reported; and (4) The probability of having photodetached electrons re-attach to form negative ions is less than 1%. Mass identifying drift tube tests confirm that the slower ion is CO3(-), formed through the O(-) + 2CO2 yields CO3(-) + CO2 reaction.

Helmy, E. M.↗
DOE OSTI2022

Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC +/0/–

A combination of high-level ab initio calculations and anion photoelectron detachment (PD) measurements is reported for the UC, UC – , and UC + molecules. To better compare the theoretical values with the experimental photoelectron spectrum (PES), a value of 1.493 eV for the adiabatic electron affinity (AEA) of UC was calculated at the Feller–Peterson–Dixon (FPD) level. The lowest vertical detachment energy (VDE) is predicted to be 1.500 eV compared to the experimental value of 1.487 ± 0.035 eV. A shoulder to lower energy in the experimental PD spectrum with the 355 nm laser can be assigned to a combination of low-lying excited states of UC – and excited vibrational states. The VDEs calculated for the low-lying excited electronic states of UC at the SO-CASPT2 level are consistent with the observed additional electron binding energies at 1.990, 2.112, 2.316, and 3.760 eV. Potential energy curves for the Ω states and the associated spectroscopic properties are also reported. Compared to UN and UN + , the bond dissociation energy (BDE) of UC (411.3 kJ/mol) is predicted to be considerably lower. The natural bond orbitals (NBO) calculations show that the UC 0/+/– molecules have a bond order of 2.5 with their ground-state configuration arising from changes in the oxidation state of the U atom in terms of the 7s orbital occupation: UC (5f 2 7s 1 ), UC – (5f 2 7s 2 ), and UC + (5f 2 7s 0 ). Furthermore, the behavior of the UN and UC sequence of molecules and anions differs from the corresponding sequences for UO and UF.

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

Photodetachment spectroscopy and resonant photoelectron imaging of cryogenically cooled 1-pyrenolate

We report an investigation of the 1-pyrenolate anion (PyO - ) and the 1-pyrenoxy radical (PyO) using photodetachment spectroscopy and resonant photoelectron imaging of cryogenically-cooled anions. The electron affinity of PyO is measured to be 2.4772(4) eV (19,980 ± 3 cm -1 ) from high-resolution photoelectron spectroscopy. Photodetachment spectroscopy reveals a dipole-bound state (DBS) for PyO - 280 cm-1 below the detachment threshold, as well as a broad and intense valence excited state (shape resonance) 1,077 cm-1 above the detachment threshold. The shape resonance with an excitation energy of 21,055 cm -1 is due to excitation of an electron from the highest occupied molecular orbital of PyO - to its lowest unoccupied molecular orbital in the continuum. Twenty-nine vibrational levels of the DBS are observed, including twenty-seven above-threshold vibrational levels (vibrational Feshbach resonances). Twenty-seven resonant photoelectron spectra are obtained by tuning the detachment laser to the vibrational Feshbach resonances, resulting in highly non-Franck-Condon photoelectron spectra and rich vibrational information. In total, the frequencies of twenty-one vibrational modes are obtained for the PyO radical by the combination of the photodetachment and resonant photoelectron spectroscopy, including thirteen out-of-plane bending modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ab initio calculations in atoms, molecules, and solids, treating spin–orbit coupling and electron interaction on an equal footing

We incorporate explicit, non-perturbative treatment of spin–orbit coupling into ab initio auxiliary-field quantum Monte Carlo (AFQMC) calculations. The approach allows a general computational framework for molecular and bulk systems in which material specificity, electron correlation, and spin–orbit coupling effects can be captured accurately and on an equal footing, with favorable computational scaling vs system size. We adopt relativistic effective-core potentials that have been obtained by fitting to fully relativistic data and that have demonstrated a high degree of reliability and transferability in molecular systems. This results in a two-component spin-coupled Hamiltonian, which is then treated by generalizing the ab initio AFQMC approach. We demonstrate the method by computing the electron affinity in Pb, the bond dissociation energy in Br 2 and I 2 , and solid Bi.

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

Design Principles of Diketopyrrolopyrrole‐Thienopyrrolodione Acceptor 1 –Acceptor 2 Copolymers

Abstract The design principles of acceptor 1 –acceptor 2 copolymers featuring alternating diketopyrrolopyrrole (DPP) and thienopyrrolodione (TPD) moieties are investigated. The investigated series of polymers is obtained by varying the aromatic linker between the two acceptor motifs between thiophene, thiazole, pyridine, and benzene. High electron affinities between 3.96 and 4.42 eV, facilitated by the synergy of the acceptor motifs are determined with optical gaps between 1.37 and 2.02 eV. Grazing incidence wide‐angle X‐ray scattering studies reveal a range of film morphologies after thermal annealing, including face‐on, end‐on and superstructure edge‐on‐like crystallites. Conversely, all materials form thin edge‐on layers on the polymer–air interface, as demonstrated by multi‐elemental near‐edge X‐ray absorption fine‐structure spectroscopy. The benefit of the electron‐deficient linkers thiazole and pyridine is evident: In organic field effect transistors, electron mobilities of up to 4.6 × 10 −2 cm 2 V −1 s −1 are obtained with outstanding on/off current ratios of 5 × 10 5 , facilitated by the absence of detectable hole transport in these materials. Viability for all‐polymer solar cells is assessed in active layer blends with the donor polymer PM6, yielding a maximum average power conversion efficiency of 4.8% and an open circuit voltage above 1 V.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Assessing the effect of regularization on the molecular properties predicted by SCAN and self-interaction corrected SCAN meta-GGA

Recent regularization of the SCAN meta-GGA functional (rSCAN) has simplified the numerical complexities of the SCAN functional, alleviating SCAN's stringent demand on the numerical integration grids to some extent. The regularization of rSCAN, however, results in the breaking of some constraints such as the uniform electron gas limit, the slowly varying density limit, and coordinate scaling of the iso-orbital indicator. Here, we assess the effects of regularization on the electronic, structural, vibrational, and magnetic properties of molecules by comparing the SCAN and rSCAN predictions. The properties studied include atomic energies, atomization energies, ionization potentials, electron affinities, barrier heights, infrared intensities, dissociation and reaction energies, spin moments of molecular magnets, and isomer ordering of water clusters. Our results show that rSCAN requires less dense numerical grids and gives very similar results to those of SCAN for all properties examined with the exception of atomization energies, which are worsened in rSCAN. We also examine the performance of self-interaction-corrected (SIC) rSCAN with respect to SIC-SCAN using the Perdew–Zunger (PZ) SIC method. The PZSIC method uses orbital densities to compute one-electron self-interaction errors and places an even more stringent demand on numerical grids. Our results show that SIC-rSCAN gives marginally better performance than SIC-SCAN for almost all properties studied in this work with numerical grids that are on average half or less as dense as that needed for SIC-SCAN.

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

Leveraging Artificial Intelligence to Predict Novel Eutectic Alloys

The goal of this project was to train an artificial neural network (ANN) to predict the fractional composition and melting point of eutectic alloys using fundamental atomic properties as inputs. The fundamental properties considered include atomic number, atomic weight, atomic radius, valence electron concentration, electronegativity, and electron affinity. The project involved several phases, starting with data preparation, where phase diagram data was harvested from the ASM International database. Approximately 1300 binary eutectics were collected and cleaned to ensure relevance and accuracy. A regression model was selected for training, utilizing a rectified linear unit as the activation function. Various model configurations were evaluated for predictive accuracy, with validation techniques employed to ensure robustness. The model demonstrated predictive capabilities above random guessing and was able to achieve up to 11% accuracy under certain conditions. An ablative test identified atomic radius and valence electron concentration as critical inputs for model performance. Incorporating the melting point of atomic constituents improved accuracy significantly, although ultimately the model’s predictive capability still fell short of the 80% target. This report details the methodology, results, and implications of the research, contributing to the understanding of employing artificial intelligence to predict the phase transition behavior of eutectic alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Solution–Doped Donor–Acceptor Copolymers Based on Diketopyrrolopyrrole and 3, 3'–Bis (2–(2–(2–Methoxyethoxy) Ethoxy) ethoxy)–2, 2'–Bithiophene Exhibiting Outstanding Thermoelectric Power Factors with p –Dopants

The design of polymeric semiconductors exhibiting high electrical conductivity (σ) and thermoelectric power factor (PF) will be vital for flexible large-area electronics. In this work, four polymers based on diketopyrrolopyrrole (DPP), 2,3-dihydrothieno[3,4-b][1,4]dioxine (EDOT), thieno[3,2-b]thiophene (TT), and 3, 3'-bis (2-(2-(2-methoxyethoxy) ethoxy) ethoxy)-2, 2'-bithiophene (MEET) are investigated as side-chains, with the MEET polymers newly synthesized for this study. These polymers are systematically doped with tetrafluorotetracyanoquinodimethane ( F 4 TCNQ), CF3SO3H, and the synthesized dopant Cp(CN) 3 -(COOMe) 3 , differing in geometry and electron affinity. The DPP-EDOT-based polymer containing MEET as side-chains exhibits the highest conductivity (σ) ≈700 S cm–1 in this series with the acidic dopant (CF 3 SO 3 H). This polymer also shows the lowest oxidation potential by cyclic voltammetry (CV), the strongest intermolecular interactions evidenced by differential scanning calorimetry (DSC), and has the most oxygen-based functionality for possible hydrogen bonding and ionic screening. Other polymers exhibit high σ ≈300–500 S cm–1 and power factor up to 300 µW m –1 K –2 . The mechanism of conductivity is predominantly electronic, as validated by time-dependent conductance studies and transient thermo voltage monitoring over time, including for those doped with the acid. Furthermore, these materials maintain significant thermal stability and air stability over ≈6 weeks. Density functional theory calculations reveal molecular geometries and inform about frontier energy levels. Raman spectroscopy, in conjunction with scanning electron microscopy (SEM-EDS) and x-ray diffraction, provides insight into the solid-state microstructure and degree of phase separation of the doped polymer films. Infrared spectroscopy enables this study to further quantify the degree of charge transfer from polymer to dopant.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Direct Characterization of Type-I Band Alignment in 2D Ruddlesden–Popper Perovskites

2D Ruddlesden–Popper halide perovskites have attracted considerable attention due to their desirable optoelectronic properties, high chemical and structural tunability, and improved environmental stability. However, the understanding of their structure–properties relationships is still limited. In particular, the energy level positions and band alignments at interfaces involving these materials, which are important features to control in the context of any applications, are still under debate. Here, the electronic structure of high-purity films of BA 2 MA n-1 Pb n I 3n+1 for n = 1–5 (where BA stands for butylammonium and MA for methylammonium) is investigated, using optical absorption, ultraviolet, and inverse photoemission spectroscopies, and density functional theory calculations. Further, this study determines the ionization energy and electron affinity of each compound and demonstrates a type-I band alignment for the BA 2 MA n-1 Pb n I 3n+1 series. This study further describes the evolution of the exciton binding energy as a function of the thickness of the inorganic layers.

2D Ruddlesden–Popper perovskites↗
DOE OSTI2025

Emission properties of a hybrid metallized diamond(001) photocathode

The spectral emission characteristics of a proof-of-concept hybrid metallized diamond(001) photocathode are presented. The quantum efficiency (QE) is shown to be determined by the photoinjection efficiency across the ohmic contact at the back metallized face, whereas the mean transverse energy (MTE) of the photoemitted electrons is consistent with an (optical)phonon-assisted and momentum-resonant Franck-Condon mechanism [Franck-Condon electron emission from polar semiconductor photocathodes, Phys. Rev. Appl. 23, 054065 (2025)] following electron drift transport to the untreated diamond(001) front emission face. Emission is observed from both the lower and upper conduction bands of diamond with positive and negative electron affinity, respectively. A potential route to the realization of a red-visible photocathode based on this concept with a sub-50 meV MTE and a QE greater than 0.1% is discussed.

Density of states↗
DOE OSTI2020

Polarizabilities of neutral atoms and atomic ions with a noble gas electron configuration

Atomic polarizabilities play an important role in the development of force fields for molecular simulations, as well as for the development of qualitative concepts of atomic and molecular behavior. Coupled cluster theory at the coupled cluster singles doubles triples level with very large correlation-consistent basis sets with extended diffuse functions has been used to predict the polarizabilities of the atomic neutrals, mono-cations and mono-anions with a noble gas configuration. Additional corrections for scalar relativistic and spin–orbit effects were also included for the electron configurations of Kr, Xe, and Rn. The results are in excellent agreement with experiment or with other high level calculations where available. The current results for most of these species represent the best available values for the polarizabilities. The results show that the polarizability of H - is very difficult to calculate without extremely diffuse functions. The polarizability of H - is the largest value, 34.05 Å 3 , calculated for all species in the current study. The polarizabilities of the remaining halogen anions are also the best available values. The polarizabilities of the halogen anions (excluding F - ) and H - have a linear correlation with the electron affinity of the neutral atom. Spin– orbit effects, even for closed shell species, cannot be ignored for quantitative accuracy, and the inclusion of spin–orbit effects for Fr + , Rn, and At - increases the polarizability by 4%, 6%, and 15%, respectively.

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

Anion photoelectron spectroscopic and relativistic coupled-cluster studies of uranyl dichloride anion, UO 2 Cl 2 –

A joint relativistic coupled-cluster and experimental photoelectron (PE) spectroscopic study of the uranyl dichloride anion, UO 2 Cl 2 – , is reported. Sophisticated electronic-structure calculations predict the photodetachment of UO 2 Cl 2 – to involve a U 5f electron and to be followed by significant geometry relaxation. Therefore, the adiabatic electron affinity (EA a ) of the uranyl dichloride neutral molecule, UO 2 Cl 2 , and the vertical detachment energy (VDE) of its anion, UO 2 Cl 2 – , provide valuable information about its uranium 5f orbital energies. The EA a value was computed to be 3.15 eV. The VDE value was calculated to be 3.55 eV by augmenting the computed EA a with a shift derived from a Franck–Condon simulation using coupled-cluster potential energy surfaces. Here, the VDE, which corresponds to the highest intensity peak in the PE spectrum, was measured to be 3.69 ± 0.20 eV, in good agreement with the computed value. The origin transition in the PE spectrum, whose electron binding energy corresponds to the EA a , was assigned to the feature at 3.2 ± 0.20 eV, consistent with the computed EA a .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Velocity-Map Imaging and Magnetic-Bottle Photoelectron Spectroscopy of [SeCCH] – : Electronic Properties and Spin–Orbit Splitting

In this work, the recently synthesized acetylide compound KSeCCH containing the main group element selenium within the novel and in crystalline form unprecedented [SeCCH] – anion was successfully investigated in the gas phase by high-resolution velocity-map imaging (VMI) and magnetic-bottle (MB) photoelectron spectroscopy coupled with an electrospray ionization source. Both VMI and MB spectra exhibited identical electron affinities (EA, 2.517 ± 0.002 eV), spin–orbit coupling (SOC) splittings (1492 ± 20 cm –1 ), and Se–C stretching frequencies (573 ± 20 cm –1 ) of the corresponding neutral tetra-atomic radical [SeCCH] • with the VMI spectrum possessing six times higher spectral resolution compared with the MB spectrum. These experimental values were well reproduced by calculations at the CCSD(T) level, in which both the isolated [SeCCH] – anion and the [SeCCH] • radical adopted linear geometries. The simulated spectra based on the calculated Franck–Condon factors, the SOC splitting, and the experimental line width matched well with the measured spectra. Furthermore, comparisons of the EA and SOC splitting values with the previously reported isolobal species [SeCN] • are also made and discussed. The decrease in the EA and SOC splitting of [SeCCH] • is ascribed to the differences in the electronegativities between C and N atoms as well as the electron density on the Se atom in its singly occupied molecular orbital (SOMO).

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

Low-Loss Charge Transfer Plasmons in Graphene/α-RuCl 3 Heterostructures Below 40 K

Charge transfer at material interfaces governs a wide range of physical properties, from electronic band structures to emergent collective excitations. In two-dimensional (2D) material heterostructures, charge transfer phenomena play important roles in enabling novel quantum phases, proximity effects, and tunable plasmonic responses. One representative charge transfer interface is formed between α-RuCl 3 , a van der Waals material with high electron affinity, and graphene. Significant charge transfer across this interface induces the formation of charge-transfer plasmon polaritons (CPPs), hybrid excitations between light and charge oscillations. However, previous studies found that as the charge transfer process takes place, α-RuCl 3 becomes lossy, which limits the quality factor of CPPs. Here, we investigate CPPs down to 10 K using a home-built scattering-type scanning near-field optical microscope (s-SNOM) optimized for low-temperature measurements. Our study reveals a dramatic suppression of plasmon loss channels below 40 K, contributing to a significant enhancement in the plasmonic quality factor. This reduction in loss is likely attributed to the blue shift of the correlation-induced Mott gap in α-RuCl 3 with decreasing temperature, along with the reduction of phonon scattering at low temperature. In conclusion, our results highlight the potential of using s-SNOM and CPPs to study complex 2D interfaces and reveal correlated electron dynamics in the underlying material.

36 MATERIALS SCIENCE↗