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At least 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Bringing weak transitions to light

Abstract Weak transitions between quantum states are of fundamental importance for a broad range of phenomena from analytical biochemistry to precision physics, but generally challenge experimental detection. Due to their small cross sections scaling with the absolute square of their transition matrix elements, spectroscopic measurements often fail in particular in the presence of competing background processes. Here we introduce a general concept to break this scaling law and enhance the transition probability by exploiting a stronger laser-coupled pathway to the same excited state. We demonstrate the concept experimentally by attosecond transient absorption spectroscopy in helium atoms. The quasi-forbidden transitions from the ground state 1s 2 to the weakly coupled doubly excited 2p3dandsp 2,4− states are boosted by an order of magnitude. Enhancing single-photon-suppressed transitions can find widespread applicability, from spectral diagnostics of complex molecules in life and chemical sciences to precision spectroscopy of weak transitions in metastable atomic nuclei in the search for new physics.

Science & Technology - Other Topics↗
DOE OSTI2024

The crystal structure of Acinetobacter baumannii bacterioferritin reveals a heteropolymer of bacterioferritin and ferritin subunits

Iron storage proteins, e.g., vertebrate ferritin, and the ferritin-like bacterioferritin (Bfr) and bacterial ferritin (Ftn), are spherical, hollow proteins that catalyze the oxidation of Fe 2+ at binuclear iron ferroxidase centers (FOC) and store the Fe 3+ in their interior, thus protecting cells from unwanted Fe 3+ /Fe 2+ redox cycling and storing iron at concentrations far above the solubility of Fe 3+ . Vertebrate ferritins are heteropolymers of H and L subunits with only the H subunits having FOC. Bfr and Ftn were thought to coexist in bacteria as homopolymers, but recent evidence indicates these molecules are heteropolymers assembled from Bfr and Ftn subunits. Despite the heteropolymeric nature of vertebrate and bacterial ferritins, structures have been determined only for recombinant proteins constituted by a single subunit type. Herein we report the structure of Acinetobacter baumannii bacterioferritin, the first structural example of a heteropolymeric ferritin or ferritin-like molecule, assembled from completely overlapping Ftn homodimers harboring FOC and Bfr homodimers devoid of FOC but binding heme. The Ftn homodimers function by catalyzing the oxidation of Fe 2+ to Fe 3+ , while the Bfr homodimers bind a cognate ferredoxin (Bfd) which reduces the stored Fe 3+ by transferring electrons via the heme, enabling Fe 2+ mobilization to the cytosol for incorporation in metabolism.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2001

Theoretical Studies of Possible Synthetic Routes for the High Energy Density Material Td N4: Excited Electronic States

Vertical electronic excitation energies for single states have been computed for the high energy density material (HEDM) Td N4 in order to assess possible synthetic routes that originate from excited electronic states of N2 molecules. Several ab initio theoretical approaches have been used, including complete active space self-consistent field (CASSCF), state averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D)) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD), which is the highest level of theory employed. Standard double zeta polarized (DZP) and triple zeta double polarized (TZ2P) one-particle basis sets were used. The CASSCF calculations are found to overestimate the excitation energies, while the SA-CASSCF approach rectifies this error to some extent, but not completely. The accuracy of the CIS calculations varied depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results are in generally good agreement. Based on the LRCCSD calculations, the lowest six excited singlet states are 9.35(l(sup)T1), 10.01(l(sup)T2), 10.04(1(sup)A2), 10.07(1(sup)E), 10.12(2(sup)T1), and 10.42(2(sup)T2) eV above the ground state, respectively. Comparison of these excited state energies with the energies of possible excited states of N2+N2 fragments, leads us to propose that the most likely synthetic route for Td N4 involving this mechanism arises from combination of two bound quintet states of N2.

Lee, Timothy J.↗
DOE OSTI2023

Triple Excitations in Green’s Function Coupled Cluster Solver for Studies of Strongly Correlated Systems in the Framework of Self-Energy Embedding Theory

Embedding theories became important approaches used for accurate calculations of both molecules and solids. In these theories, a small chosen subset of orbitals is treated with an accurate method, called an impurity solver, capable of describing higher correlation effects. Ideally, such a chosen fragment should contain multiple orbitals responsible for the chemical and physical behavior of the compound. Handling a large number of chosen orbitals presents a very significant challenge for the current generation of solvers used in the physics and chemistry community. Here, we develop a Green’s function coupled cluster singles doubles and triples (GFCCSDT) solver that can be used for a quantitative description in both molecules and solids. This solver allows us to treat orbital spaces that are inaccessible to other accurate solvers. At the same time, GFCCSDT maintains high accuracy of the resulting self-energy. Moreover, in conjunction with the GFCCSD solver, it allows us to test the systematic convergence of computational studies. Developing the CC family of solvers paves the road to fully systematic Green’s function embedding calculations in solids. In this paper, we focus on the investigation of GFCCSDT self-energies for a strongly correlated problem of SrMnO 3 solid. Subsequently, we apply this solver to solid MnO showing that an approximate variant of GFCCSDT is capable of yielding a high accuracy orbital resolved spectral function.

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

Direct Observation of Solvent–Reaction Intermediate Interactions in Heterogeneously Catalyzed Alcohol Coupling

The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid phases, is dependent on numerous factors. One well-established example is secondary interactions, such as van der Waals interactions between the catalyst surface and the pendant group of the intermediate, which can govern reaction selectivity for coupling reactions. In this work, we directly show that interactions between adsorbed reaction intermediates and reactant molecules increase the binding energy and affects the geometrical arrangement of coadsorbed reactant/solvent molecules. Evidence for this effect is demonstrated for the oxidative coupling reaction of methanol on a single crystal gold (Au(110)) surface. The rate-limiting reaction intermediate for methanol selfcoupling, methoxy, stabilizes excess adsorbed methanol, which desorbs as a result of beta-hydride decomposition of the adsorbed methoxy. Direct molecular-scale imaging by scanning tunneling microscopy, supplemented by density functional theory, revealed interactive structures formed by methoxy and coadsorbed methanol. Interactions between the methoxy intermediate and coadsorbed methanol stabilizes a hydrogen-bonded network comprising methoxy and methanol by a minimum of 0.13 eV per methanol molecule. Inclusion of such interactions between reaction intermediates and coadsorbed reactants and solvents in kinetic models is important for microkinetic analysis of the rates and selectivities of catalytic reactions in both the gas and liquid phases whenever appreciable coverages of species from the ambient phase exist.

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

Multivalent optical cycling centers: towards control of polyatomics with multi-electron degrees of freedom

Optical control of polyatomic molecules promises new opportunities in precision metrology and fundamental chemistry, as well as quantum information and many-body science. Contemporary experimental and theoretical efforts have mostly focused on cycling photons via excitation of a single electron localized to an alkaline earth (group 2)-like metal center. In this paper, we consider pathways towards optical cycling in polyatomic molecules with multi-electron degrees of freedom, which arise from two or more cycling electrons localized to p-block post-transition metal and metalloid (group 13, 14, and 15) centers. Here, we characterize the electronic structure and rovibrational branching of several prototypical candidates using ab initio quantum chemical methods. Despite increased internal complexity and challenging design parameters, we find several molecules possessing quasi-closed photon cycling schemes with highly diagonal, visible and near-infrared transitions. Furthermore, we identify new heuristics for engineering optically controllable and laser-coolable polyatomic molecules with multi-electron cycling centers. Our results help elucidate the interplay between hybridization, repulsion, and ionicity in optically active species and provide new directions for using polyatomic molecules with complex electronic structure as a resource for quantum science and measurement.

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

Imaging Valence Electron Rearrangement in a Chemical Reaction Using Hard X-Ray Scattering

We have observed the signatures of valence electron rearrangement in photoexcited ammonia using ultrafast hard x-ray scattering. Time-resolved x-ray scattering is a powerful tool for imaging structural dynamics in molecules because of the strong scattering from the core electrons localized near each nucleus. Such core-electron contributions generally dominate the differential scattering signal, masking any signatures of rearrangement in the chemically important valence electrons. Ammonia represents an exception to the typically high core-to-valence electron ratio. Here, we measured 9.8 keV x-ray scattering from gas-phase deuterated ammonia following photoexcitation via a 200 nm pump pulse to the 3s Rydberg state. We observed changes in the recorded scattering patterns due to the initial photoexcitation and subsequent deuterium dissociation. Ab initio calculations confirm that the observed signal is sensitive to the rearrangement of the single photoexcited valence electron as well as the interplay between adiabatic and nonadiabatic dissociation channels. The use of ultrafast hard x-ray scattering to image the structural rearrangement of single valence electrons constitutes an important advance in tracking valence electronic structure in photoexcited atoms and molecules.

Gabalski, Ian [SLAC National Accelerator Laborator↗
DOE OSTI2021

Vibrational spectroscopy of uranium tetrafluoride hydrates

Uranium tetrafluoride (UF 4 ) is an important intermediate in the production of UF6 and nuclear fuel. Historical characterization of UF 4 with Raman spectroscopy was plagued with ambiguity until the first accurate Raman spectrum was published by our group in 2016. Although generally considered to be relatively stable, UF 4 can hydrolyze to form numerous UF 4 hydrates that may play a role in future uranium waste forms. In contrast to anhydrous UF 4 , the hydrates, with their OH stretch and HOH bending modes, can be spectroscopically characterized by the type and degree of water bonding in the crystal lattice, which can yield additional information about their crystal structure. Herein, vibrational spectroscopy (Raman and infrared) was used to characterize three different UF 4 hydrates: UF 4 (H 2 O) 0.33 , U 3 F 12 (H 2 O), and UF 4 (H 2 O) 2.5 . Spectra show the different hydrates vary in the number of observed bands, full-width half-maximum of the bands, and band intensity. These differences are due to varying interactions between the OH stretch and HOH bending modes with UF 4 and the polymeric UF 4 structure in the crystal lattice. These vibrational data, in combination with spectral fitting and crystallographic structures measured with powder X-ray diffraction and single crystal X-ray diffraction, provide unique details on the location of water molecules in the crystal lattice of hydrated UF 4 , and provide an interesting contrast to the vibrational spectra of anhydrous UF 4 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Graphene nanoribbons initiated from molecularly derived seeds

Abstract Semiconducting graphene nanoribbons are promising materials for nanoelectronics but are held back by synthesis challenges. Here we report that molecular-scale carbon seeds can be exploited to initiate the chemical vapor deposition (CVD) synthesis of graphene to generate one-dimensional graphene nanoribbons narrower than 5 nm when coupled with growth phenomena that selectively extend seeds along a single direction. This concept is demonstrated by subliming graphene-like polycyclic aromatic hydrocarbon molecules onto a Ge(001) catalyst surface and then anisotropically evolving size-controlled nanoribbons from the seeds along $$\left\langle 110\right\rangle$$ 110 of Ge(001) via CH 4 CVD. Armchair nanoribbons with mean normalized standard deviation as small as 11% (3 times smaller than nanoribbons nucleated without seeds), aspect ratio as large as 30, and width as narrow as 2.6 nm (tunable via CH 4 exposure time) are realized. Two populations of nanoribbons are compared in field-effect transistors (FETs), with off-current differing by 150 times because of the nanoribbons’ different widths.

36 MATERIALS SCIENCE↗
DOE OSTI2023

On the potentially transformative role of auxiliary-field quantum Monte Carlo in quantum chemistry: A highly accurate method for transition metals and beyond

Approximate solutions to the ab initio electronic structure problem have been a focus of theoretical and computational chemistry research for much of the past century, with the goal of predicting relevant energy differences to within “chemical accuracy” (1 kcal/mol). For small organic molecules, or in general, for weakly correlated main group chemistry, a hierarchy of single-reference wave function methods has been rigorously established, spanning perturbation theory and the coupled cluster (CC) formalism. For these systems, CC with singles, doubles, and perturbative triples is known to achieve chemical accuracy, albeit at O(N7) computational cost. In addition, a hierarchy of density functional approximations of increasing formal sophistication, known as Jacob’s ladder, has been shown to systematically reduce average errors over large datasets representing weakly correlated chemistry. However, the accuracy of such computational models is less clear in the increasingly important frontiers of chemical space including transition metals and f-block compounds, in which strong correlation can play an important role in reactivity. A stochastic method, phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC), has been shown to be capable of producing chemically accurate predictions even for challenging molecular systems beyond the main group, with relatively low O(N3 − N4) cost and near-perfect parallel efficiency. Herein, we present our perspectives on the past, present, and future of the ph-AFQMC method. We focus on its potential in transition metal quantum chemistry to be a highly accurate, systematically improvable method that can reliably probe strongly correlated systems in biology and chemical catalysis and provide reference thermochemical values (for future development of density functionals or interatomic potentials) when experiments are either noisy or absent. Finally, we discuss the present limitations of the method and where we expect near-term development to be most fruitful.

Chemistry↗
DOE OSTI2023

Direct momentum imaging of charge transfer following site-selective ionization

We study ultrafast charge rearrangement in dissociating 2-iodopropane (2-C 3 H 7 I) using site-selective core-ionization at the iodine atom. Clear signatures of electron transfer between the neutral propyl fragment and multiply charged iodine ions are observed in the recorded delay-dependent ion momentum distributions. The detected charge transfer pathway is only favorable within a small (few angstrom), charge-state-dependent spatial window located at C-I distances longer than that of the neutral ground-state molecule. Lastly, these results offer new insights into the physics underpinning charge transfer in isolated molecules and pave the way for a new class of time-resolved studies.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Two-dimensional multifunctional materials from endohedral fullerenes

A multifunctional two-dimensional (2D) material is theoretically predicted based on systematic ab initio calculations and model simulations for the honeycomb lattice of endohedral fullerene W@C 28 molecules. It has structural bistability, ferroelectricity, multiple magnetic phases, and excellent valley characters and can be easily functionalized by the proximity effect with magnetic isolators such as MnTiO 3 . Furthermore, we may also manipulate the valley Hall and spin transport properties by selectively switching a few W@C 28 molecules to the metastable phase. These conclusions contribute to integrating different functions in a single 2D material for technological innovations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Understanding the Interactions of Seawater Ions with Amidoxime through X-Ray Crystallography

Insoluble polymer substrates functionalized with the amidoxime (R-C(NH 2 )=NOH) functional group have been demonstrated as a technically feasible platform for extracting uranium from seawater, a potential source of extremely abundant uranium for use as nuclear fuel. While it is possible to isolate macroscopic amounts of uranium from the ocean with a positive energy return on investment using these materials, both the economic and energetic costs are many times greater than those of terrestrial uranium mining. Currently, the major contribution to this cost is the production of the sorbent itself, so being able to recycle the sorbent even a small number of times will have a huge impact on lowering the cost of their use. However, amidoxime resins show capacity fading when stripped by strong acids, presently limiting their recyclability. Both alternative extractants and alternative elution chemistries are under development with promising results but are yet at too early a stage to make predictions about their ultimate success. Given the potentially huge impact of a successful recycling process on the viability of seawater extraction of uranium, there is a strong need to pursue additional routes to elution chemistry. During the course of this project, we studied the interactions of amidoxime-containing small molecules with the abundant metal ions in seawater, including Li, Na, K, Mg, Ca, Fe, Cu, and V, to understand the interactions of [UO 2 ] 2+ with amidoxime. By using small molecules with multiple adjacent functional groups, we crystallized the resulting metal complexes and used single crystal X-ray diffraction (SCXRD) as our primary tool for structural characterization. We also investigated the use of solutions of hydroxylammonium salts in weak acids as eluents for stripping and recycling amidoxime-based sorbents. The replacement of strong acids, which react with and destroy the amidoxime functional groups, with weak acids based on hydroxylammonium, a reagent that is actually used to make the amidoxime groups, is expected to avoid capacity loss on recycling and possibly even regenerate functionality that was lost due to exposure to the marine environment.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1987

A simple interpretation of the Fe2(-) photoelectron spectrum

The photoelectron spectrum of Fe2(-) can be simply interpreted in terms of electron detachment from the mildly bonding 4s sigma sup * sub u orbital of a (4s sigma sub s)(sup 2) (4s sigma sup * sub u)(sup 2) (3d)(sup 13) anion. This interpretation implies a (4s sigma sub g)(sup 2) (4s sigma sup * sub u)(sup1) (3d)(sup13) configuration for the ground state of Fe2, correlating with one ground state (4s2 3d6) and one excited state (4s1 3d7) Fe atom. A comparison of the bond length and vibrational frequency of Fe2 to values for transition metal dimers containing single 4s-4s bonds is suggestive of 3d-3d bonding in this molecule. The results of preliminary full-valence configuration interaction calculations provide stron support for the proposed Fe2 and Fe2(-) configurations.

Leopold, Doreen G.↗
NASA NTRS2004

Monte Carlo Technique Used to Model the Degradation of Internal Spacecraft Surfaces by Atomic Oxygen

Atomic oxygen is one of the predominant constituents of Earth's upper atmosphere. It is created by the photodissociation of molecular oxygen (O2) into single O atoms by ultraviolet radiation. It is chemically very reactive because a single O atom readily combines with another O atom or with other atoms or molecules that can form a stable oxide. The effects of atomic oxygen on the external surfaces of spacecraft in low Earth orbit can have dire consequences for spacecraft life, and this is a well-known and much studied problem. Much less information is known about the effects of atomic oxygen on the internal surfaces of spacecraft. This degradation can occur when openings in components of the spacecraft exterior exist that allow the entry of atomic oxygen into regions that may not have direct atomic oxygen attack but rather scattered attack. Openings can exist because of spacecraft venting, microwave cavities, and apertures for Earth viewing, Sun sensors, or star trackers. The effects of atomic oxygen erosion of polymers interior to an aperture on a spacecraft were simulated at the NASA Glenn Research Center by using Monte Carlo computational techniques. A two-dimensional model was used to provide quantitative indications of the attenuation of atomic oxygen flux as a function of the distance into a parallel-walled cavity. The model allows the atomic oxygen arrival direction, the Maxwell Boltzman temperature, and the ram energy to be varied along with the interaction parameters of the degree of recombination upon impact with polymer or nonreactive surfaces, the initial reaction probability, the reaction probability dependence upon energy and angle of attack, degree of specularity of scattering of reactive and nonreactive surfaces, and the degree of thermal accommodation upon impact with reactive and non-reactive surfaces to be varied to allow the model to produce atomic oxygen erosion geometries that replicate actual experimental results from space. The degree of erosion of various interior locations was compared with the erosion that would occur external to the spacecraft. Results of one cavity model indicate that, at depths into a two-dimensional cavity that are equal to 10 cavity widths, the erosion on the walls of the cavity is less than that on the top surface by over 2 orders of magnitude. Wall erosion near the surface of a cavity depends on which wall is receiving direct atomic oxygen attack. However, deep in the cavity little difference is present. Testing of various cavity models such as these gives spacecraft designers an indication of the level of threat to sensitive interior surfaces for different geometries. Even though the Monte Carlo model is two-dimensional, it can be used to provide qualitative information about spacecraft openings that are three-dimensional by offering reasonable insight as to the nature of the attenuation of damage that occurs within a spacecraft in low Earth orbit. As shown, there is more erosion on the side seeing direct atomic oxygen attack until a depth of approximately 5 times the width of the opening, where the erosion is the same on both sides.

Banks, Bruce A.↗
NASA NTRS2018

Infrared Band Strengths for Amorphous and Crystalline Methyl Propionate, a Candidate Interstellar Molecule

Mid-infrared spectra of amorphous and crystalline methyl propionate, CH3CH2COOCH3, are presented for the first time from a single laboratory, along with measurements of the refractive index of each solid form. Density estimates are made and IR band strengths and absorption coefficients are calculated. Vapor pressures of crystalline methyl propionate at 140-150 K are reported along with an enthalpy of sublimation. Spectroscopic results are compared to a recent study of this compound, and the phase of methyl propionate in that work is identified. Several applications are described.

Astrochemistry↗
DOE OSTI2020

Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts

Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research

Dagle, Vanessa↗