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At least 523 records · Page 29

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DOE OSTI2025

Insights from designing an artificial cascade catalysis system using principles from substrate channeling in enzymes

Generalizing the key requirements of highly-selective, multi-step chemical conversions involving spatially separated reaction centers remains one of the grand challenges of chemistry. Much work towards this effort has focused on decomposing multi-step conversions into their constituent reactions, whose intermediates are successively upgraded in a chemical cascade via diffusion from center to center. This approach for synthesizing more complex molecules takes its cues from biochemical networks, where near-unit conversion of even complex carbohydrates is achieved by upgrading chemical precursors via enzymatic cascades. In this computational study we examine a simple cascade involving coupled Ag and Cu catalysts that sequentially converts CO2 to CO and then CO2 and CO to reduced products, generically named CO2Product and COProduct. The system architecture is inspired by the phenomenon of biological substrate channeling, and components are examined to evaluate their effects on conversion efficiency in the cascade. Aside from a substrate channel linking two reaction centers, we find efficient cascades must also incorporate directional substrate diffusion, compartmentalization of the reaction centers, and proper timing of substrate arrival at the active center. We make explicit linkages between these requirements and chemical conversion in known biological systems, revealing additional control elements that could be incorporated.

CO 2 reduction↗

DOE OSTI2025

Comparison of Ce( iv )/Th( iv )-alkynyl complexes and observation of a trans -influence ligand series for Ce( iv )

Organometallic cerium(iv) complexes have been challenging to isolate and characterize due to the strongly oxidizing nature of the cerium(iv) cation. Herein, we report two cerium(iv) alkynyl complexes, [Ce(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-CeTMS) and [Ce(TriNOx)(C[triple bond, length as m-dash]C-Ph)] (1-CePh) (TriNOx3- = tris(2-tert-butylhydroxylaminato)benzylamine), that include terminal alkyne moieties. The isostructural thorium analogue [Th(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-ThTMS) was also synthesized and compared with 1-CeTMS in bond distance, 13C-NMR spectra, vibrational spectra and electronic structure. The Ce-C bond distances were 2.501(3) Å for 1-CePh and 2.513(5) Å for 1-CeTMS on the shorter end of the few reported CeIV-C single bonds (2.478(3)-2.705(2) Å), possibly indicating significant Ce 5d- and 4f-orbital involvement. 13C-NMR spectroscopy was also consistent with Ce-C covalency, with significantly deshielded resonances ranging from 185-213 ppm. Such 13C-NMR shifts demonstrate a strong influence from spin-orbit coupling (SOC) effects, corroborated by computational studies. Raman analysis showed ν C[triple bond, length as m-dash]C stretching frequencies of 2000 cm-1 (1-CeTMS) and 2052 cm-1 (1-CePh), indicating the cerium(iv)-alkynyl interaction, compared to the parent HC[triple bond, length as m-dash]CPh (IR = 2105 cm-1 and Raman = 2104 cm-1). L3-edge X-ray absorption measurements revealed a predominant Ce(iv) electronic configuration, and magnetic measurements revealed temperature-independent paramagnetism. Electrochemical studies similarly revealed the electron donating ability of the alkynyl ligands, stronger than either fluoride or imido ligands for the Ce(iv)(TriNOx)-framework, with a cerium(iv/iii) reduction potential of E pc = -1.58 to -1.66 V vs. Fc/Fc+. Evidence for a trans-influence has been observed by evaluating a series including previously reported [CeIV(TriNOx)X]+/0 complexes with axial ligands X = THF, I-, Br-, Cl-, F-, -C[triple bond, length as m-dash]C-Ph, -C[triple bond, length as m-dash]C-SiMe3, -NH(3,5-(CF3)2-Ar), -OSiPh3, -N(M(L))(3,5-(CF3)2-Ar) [M(L) = Li(TMEDA), K(DME)2 or Cs(2,2,2-crypt)]. These data stand in contrast with previous reports of an inverse trans-influence at cerium(iv) and point to differences in involvement of cerium 4f- versus 5d-orbitals in the electronic structures of the complexes.

Yang, Qiaomu↗

DOE OSTI2025

Come for predictions, stay for complexity: synthesis and experimental probing of ionic conductivity in Li 9 B 19 S 33

Lithium thioborates, despite their potential cost-effectiveness and low density, have received considerably less attention as solid electrolytes compared to their thiophosphate counterparts. A primary obstacle to their widespread investigation has been the inherent challenge in synthesizing single-phase materials. Computational studies have predicted several lithium thioborate phases exhibiting high ionic conductivity, with Li 9 B 19 S 33 notably predicted to reach 80 mS cm −1 . However, experimental validation of these theoretical predictions remains absent. This work addresses this gap by detailing a successful synthesis of the previously elusive Li 9 B 19 S 33 phase, facilitated by in situ temperature dependent powder X-ray diffraction. Our findings reveal the peritectic nature of phase formation, necessitating an excess of boron sulfide in the reaction mixture. We further present a comprehensive structural characterization of Li 9 B 19 S 33 utilizing spectroscopic techniques like NMR, FT-IR, and diffuse reflectance and report on its ionic conductivity. Solid-state 6 Li NMR line narrowing experiments revealed an ion mobility activation energy of 0.26 eV whereas activation energies derived from impedance spectroscopy measurements were significantly higher, resulting in lower than theoretically predicted ionic conductivity.

Oppong, Richeal A. [Iowa State Univ., Ames, IA (Un↗

DOE OSTI2025

Capacity Design Method for Integrated Convective/Radiant Terminals to Guarantee Overall and Local Environment

To achieve energy efficiency in the operation of heating devices and ensure thermal comfort in indoor environments, the integrated convective/radiant terminals have become an important development direction for heating systems. This study selected a 14 m 2 bedroom hot summer and cold winter region in China as a case study. Computational Fluid Dynamics (CFD) methodology was used to investigate the design of integrated convective/radiant terminals to ensure thermal comfort for both the entire room and partial space. The results indicate that focusing on partial space during the steady-state stage can achieve energy savings of 31.1% compared to guaranteeing the entire room. Additionally, during the start-up stage, there is a significant reduction of convective unit capacity by 17.6% when the start-up time is 15 minutes. These findings provide data support for the design and engineering applications of products of integrated convective/radiant terminals. Besides, the excess convection ratios for the entire room and partial space are specified as 0.69 to 0.80 and 0.73 to 0.83, respectively.

Chi, Junjie↗

DOE OSTI2020

Computational modeling of charge hopping dynamics along a disordered one-dimensional wire with energy gradients in quantum environments

This computational study investigates the effects of energy gradients on charge hopping dynamics along a one-dimensional chain of discrete sites coupled to quantum bath, which is modeled at the level of Pauli master equation (PME). This study also assesses the performance of different approximations for the hopping rates. Three different methods for solving the PME, a fourth order Runge–Kutta method, numerical diagonalization of the rate matrix followed by analytic propagation, and kinetic Monte Carlo simulation method, are tested and confirmed to produce virtually identical values of time dependent mean square displacement, diffusion constant, and mobility. Five different rate expressions, exact numerical evaluation of Fermi’s Golden Rule (FGR) rate, stationary phase interpolation (SPI) approximation, semiclassical approximation, classical Marcus rate, and Miller–Abrahams rate, are tested to help understand the effects of approximations in representing quantum environments in the presence of energy gradients. The results based on direct numerical evaluation of FGR rate exhibit transition from diffusive to non-diffusive behavior with the increase in the gradient and show that the charge transport in the quantum bath is more sensitive to the magnitude of the gradient and the disorder than in the classical bath. Among all the four approximations for the hopping rates, the SPI approximation is confirmed to work best overall. A comparison of two different methods to calculate the mobility identifies drift motion of the population distribution as the major source of non-diffusive behavior and provides more reliable information on the contribution of quantum bath.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Ultrafast hole transfer from monolayer ReS 2 to thin-film F 8 ZnPc

We report a combined experimental and computational study on the charge transfer properties of heterostructures formed by monolayer 1T’-ReS 2 and fluorinated zinc phthalocyanine, F 8 ZnPc. Two-dimensional (2D) ReS 2 monolayer flakes were exfoliated from bulk crystals, and a F 8 ZnPc film with a thickness of 4 nm was thermally deposited on ReS 2 . Density functional theory shows that the two materials form a type-II band alignment. In transient absorption measurements, photocarriers are selectively excited in ReS 2 and monitored in F 8 ZnPc. Here, we found that holes in ReS 2 can transfer to F 8 ZnPc on a time scale shorter than 0.35 ps. The transferred holes have a long lifetime in F 8 ZnPc on the order of 1 ns, confirming the lack of electron transfer. The efficient charge transfer from a 1T’ transition metal dichalcogenide monolayer to an organic semiconductor illustrates the feasibility of developing 2D/organic heterostructures with in-plane anisotropic electronic and optoelectronic properties.

2D materials↗

DOE OSTI2022

Energy, angle, and temperature dependencies of the sticking of D atoms on Li surfaces

Detailed experimental and computational information on the response of lithium surfaces to irradiation by slow hydrogenic particles (ions, atoms, molecules) is sparse and mainly speculative. In this work, we present a computational study of the reflection and retention of deuterium (D) atoms at crystalline and amorphous lithium surfaces at 300 and 500 K, where the D atoms have an impact energy in the range of 0.025–5 eV and incident angles of 0° (perpendicular incidence) or 85° (near-grazing incidence). Classical molecular dynamics simulations are performed with the reactive bond-order force field (ReaxFF) potentials. This study provides quantitative information on the deuterium sticking probability and recycling coefficient for lithium surfaces. Further, our results support the ongoing work at the Lithium Tokamak eXperiment-β fusion experiment as well as relevant experiments in the laboratory setting.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2023

How generic is iodide-tagging photoelectron spectroscopy: An extended investigation on the Gly· X - (Gly = glycine, X = Cl or Br) complexes

We report a joint negative ion photoelectron spectroscopy (NIPES) and quantum chemical computational study on glycine-chloride/bromide complexes (denoted Gly·X - , X = Cl/Br) in close comparison to the previously studied Gly·I - cluster ion. Combining experimental NIPE spectra and theoretical calculations, various Gly·X - complexes were found to adopt the same types of low-lying isomers, albeit with different relative energies. Despite more congested spectral profiles for Gly·Cl - and Gly·Br - , spectral assignments were accomplished with the guidance of the knowledge learned from Gly·I - , where a larger spin–orbit splitting of iodine afforded well-resolved, recognizable spectral peaks. Three canonical plus one zwitterionic isomer for Gly·Cl - and four canonical conformers for Gly·Br - were experimentally identified and characterized in contrast to the five canonical ones observed for Gly·I - under similar experimental conditions. Taken together, this study investigates both genericity and variations in binding patterns for the complexes composed of glycine and various halides, demonstrating that iodide-tagging is an effective spectroscopic means to unravel diverse ion-molecule binding motifs for cluster anions with congested spectral bands by substituting the respective ion with iodide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Neutral gas pressure dependence of ion–ion mutual neutralization rate constants using Landau–Zener theory coupled with trajectory simulations

In this computational study, we describe a self-consistent trajectory simulation approach to capture the effect of neutral gas pressure on ion–ion mutual neutralization (MN) reactions. The electron transfer probability estimated using Landau–Zener (LZ) transition state theory is incorporated into classical trajectory simulations to elicit predictions of MN cross sections in vacuum and rate constants at finite neutral gas pressures. Electronic structure calculations with multireference configuration interaction and large correlation consistent basis sets are used to derive inputs to the LZ theory. The key advance of our trajectory simulation approach is the inclusion of the effect of ion-neutral interactions on MN using a Langevin representation of the effect of background gas on ion transport. For H + – H – and Li + – H(D) – , our approach quantitatively agrees with measured speed-dependent cross sections for up to ~10 5 m/s. For the ion pair Ne + – Cl – , our predictions of the MN rate constant at ~1 Torr are a factor of ~2 to 3 higher than the experimentally measured value. Similarly, for Xe + – F – in the pressure range of ~20 000–80 000 Pa, our predictions of the MN rate constant are ~20% lower but are in excellent qualitative agreement with experimental data. Here, the paradigm of using trajectory simulations to self-consistently capture the effect of gas pressure on MN reactions advanced here provides avenues for the inclusion of additional nonclassical effects in future work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Learning the stable and metastable phase diagram to accelerate the discovery of metastable phases of boron

Boron, an element of captivating chemical intricacy, has been surrounded by controversies ever since its discovery in 1808. The complexities of boron stem from its unique position between metals and insulators in the Periodic Table. Recent computational studies have shed light on some of the stable boron allotropes. However, the demand for multifunctionality necessitates the need to go beyond the stable phases into the realm of metastability and explore the potentially vast but elusive metastable phases of boron. Traditional search for stable phases of materials has focused on identifying materials with the lowest enthalpy. Here, we introduce a workflow that uses reinforcement learning coupled with decision trees, such as Monte Carlo tree search, to search for stable and metastable boron phases, with enthalpy as the objective. We discover new boron metastable phases and construct a phase diagram that locates their phase space (T, P) at different levels of metastability (ΔG) from the ground state and provides useful information on the domains of relative stability of the various stable and metastable boron phases.

42 ENGINEERING↗

DOE OSTI2024

Deprotonated sulfamic acid and its homodimers: Does sulfamic acid adopt zwitterion during cluster growth?

Here we present a joint experimental and computational study on the geometric and electronic structures of deprotonated sulfamic acid (SA) clusters [(SA) n –H] – (n = 1, 2) employing negative ion photoelectron spectroscopy and high-level ab initio calculations. The photoelectron spectra provide the vertical/adiabatic detachment energy (VDE/ADE) of the sulfamate anion (SM – ) H 2 N•SO 3 – at 4.85 ± 0.05 and 4.58 ± 0.08 eV, respectively, and the VDE and ADE of the SM – •SA dimer at 6.41 ± 0.05 and 5.87 ± 0.08 eV, respectively. The significantly increased electron binding energies of the dimer confirm the enhanced electronic stability upon the addition of one SA molecule. The CCSD(T)-predicted VDEs/ADEs agree excellently with the experimental data, confirming the identified structures as the most stable ones. Two types of dimer isomers possessing different hydrogen bonding (HB) motifs are identified, corresponding to SM – binding to a zwitterionic SA (SM – •SA z ) and a canonical SA (SM – •SA c ), respectively. Two N–H$\cdots$O HBs and one superior O–H$\cdots$O HB are formed in the lowest-lying SM – •SA c , while SM – •SA z has three moderate N–H$\cdots$O HBs, with the former being 4.71 kcal/mol more stable. Further theoretical analyses reveal that the binding strength advantage of SM – •SA c over SM – •SA z arises from its significant contributions of orbital interactions between fragments, illustrating that sulfamate strongly interacts with its parent SA acid and preferably chooses the canonical SA in the subsequent cluster formations. Given the prominent presence of SA, this study provides the first evidence that the canonical dimer model of sulfamic acid should exist as a superior configuration during cluster growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Compositionally complex carbide ceramics: A perspective on irradiation damage

Extensive experimental and computational studies have demonstrated outstanding physical and chemical properties of the novel materials of compositionally complex carbides (CCCs), enabling their promising applications in advanced fission and fusion energy systems. This perspective provides a comprehensive overview of radiation damage behavior reported in the literature to understand the fundamental mechanisms related to the impact of multi-principal metal components on phase stability, irradiation-induced defect clusters, irradiation hardening, and thermal conductivity of compositionally complex carbides. Several future research directions are recommended to critically evaluate the feasibility of designing and developing new ceramic materials for extreme environments using the transformative “multi-principal component” concept. Compared to the existing materials for nuclear applications including stainless steels, nickel alloys, ZrC, SiC, and potentially high-entropy alloys, as well as certain other compositionally complex ceramic families. CCCs appear to be more resistant to amorphization, growth of irradiation defect clusters, and void swelling.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Calculation of ion–ion mutual neutralization rate constants using Landau–Zener theory coupled with trajectory simulations for Ar + –Cl − , Br − , I −

In this computational study, we self-consistently calculate the rate constants of mutual neutralization reactions by incorporating the electron transfer probability, using Landau–Zener state transition theory with inputs derived from ab initio quantum chemistry calculations, into classical trajectory simulations. Electronic structure calculations are done using correlation consistent basis sets with multi-reference configuration interaction to map all the molecular electronic states below the ion-dissociation limit as a function of the distance between the reacting species. Our electronic structure calculations have been significantly improved from our previous work through improved selection of molecular electronic configurations maintaining a fine grid of 1a 0 over a wide range of bond lengths and accurate treatment of spin–orbit couplings. Non-adiabatic coupling matrix elements are calculated with the three-point central difference method near each avoided crossing to estimate the exact crossing point R x and coupling parameter H if , which are inputs to the multi-channel Landau–Zener theory to calculate the electron transition probability. Our approach is applied to estimate the mutual neutralization rate constants for the following ion pairs: Ar + –Cl − , Ar + –Br − , Ar + –I − at ∼133 Pa. Furthermore, our predictions are compared against the experimental data reported. It is seen that the improvement in the electronic structure calculation results in excellent agreement between the simulation results and the available experimental data to within a factor of ∼2 or ∼±50%.

Complete-active space self-consistent field↗

DOE OSTI2025

Effect of nozzle translation on a bounded vortex flow

A bounded vortex flow is generated by a nozzle that combines azimuthally tilted downward jets in a circular array and a central suction port. When the nozzle is directed toward a bottom surface (called the impingement surface), the flow develops a strong intake vortex spanning from the impingement surface to the suction port, which acts to generate strong shear stress on the impingement surface. This strong shear stress can aid in removing particles attached to the impingement surface or in enhancement of heat or mass transfer, where in typical applications, the nozzle would be translated along the impingement surface. This paper reports on a computational study of the effect of nozzle translation on the bounded vortex flow field. The nozzle translation induces a bending of the bounded vortex in the downstream flow direction, which becomes larger with increase in the nozzle translation speed. We identify an interesting oscillatory phenomenon by which the bounded vortex can resist the bending induced by the translational flow and rotate about a mean position downstream of the suction port. At sufficiently high translation speeds, the oscillatory process can no longer resist the downwash effect from nozzle translation and the vortex eventually detaches from the impingement surface, limiting the effectiveness of this flow device.

42 ENGINEERING↗

DOE OSTI2021

Cryo-EM structures of Escherichia coli cytochrome bo 3 reveal bound phospholipids and ubiquinone-8 in a dynamic substrate binding site

Two independent structures of the proton-pumping, respiratory cytochrome bo3 ubiquinol oxidase (cyt bo 3 ) have been determined by cryogenic electron microscopy (cryo-EM) in styrene–maleic acid (SMA) copolymer nanodiscs and in membrane scaffold protein (MSP) nanodiscs to 2.55- and 2.19-Å resolution, respectively. The structures include the metal redox centers (heme b, heme o 3 , and Cu B ), the redox-active cross-linked histidine–tyrosine cofactor, and the internal water molecules in the proton-conducting D channel. Each structure also contains one equivalent of ubiquinone-8 (UQ8) in the substrate binding site as well as several phospholipid molecules. The isoprene side chain of UQ8 is clamped within a hydrophobic groove in subunit I by transmembrane helix TM0, which is only present in quinol oxidases and not in the closely related cytochrome c oxidases. Both structures show carbonyl O1 of the UQ8 headgroup hydrogen bonded to D75I and R71 I . In both structures, residue H98 I occupies two conformations. In conformation 1, H98 I forms a hydrogen bond with carbonyl O4 of the UQ8 headgroup, but in conformation 2, the imidazole side chain of H98 I has flipped to form a hydrogen bond with E14 I at the N-terminal end of TM0. We propose that H98 I dynamics facilitate proton transfer from ubiquinol to the periplasmic aqueous phase during oxidation of the substrate. Computational studies show that TM0 creates a channel, allowing access of water to the ubiquinol headgroup and to H98 I .

bioenergetics↗

DOE OSTI2021

Combining pressure and electrochemistry to synthesize superhydrides

Significance Superhydrides are a materials system where near–room-temperature superconductivity has been achieved but only at very high (megabar) pressures. This work proposes an approach that combines pressure and electrochemistry to stabilize superhydrides at moderate pressures. Through a computational study of the palladium–hydrogen system, we construct electrochemical phase diagrams and show that electrochemically synthesizing superhydrides may be possible when combined with moderate pressures. We generalize this to other binary metal superhydrides of interest for superconductivity, including La, Y, and Mg hydrides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Hydrogen ejection from hydrocarbons: Characterization and relevance in soot formation and interstellar chemistry

Polycyclic aromatic hydrocarbons (PAHs) play a major role in the chemistry of combustion, pyrolysis, and the interstellar medium. Production (or activation) of radical PAHs and propagation of their resulting reactions require efficient dehydrogenation, but the preferred method of hydrogen loss is not well understood. Unimolecular hydrogen ejection (i.e., direct C─H bond fission) and bimolecular radical abstraction are two main candidate pathways. We performed a computational study to characterize the role of H ejection, particularly as a driver for radical-centric hydrocarbon-growth mechanisms and particle formation. Electronic structure calculations establish that C─H bond strengths span a broad range of energies, which can be weaker than 30 kcal/mol in some C 9 and C 13 PAH radicals. At T > 1200 K, calculated thermal rates for hydrogen ejection from weak C─H bonds at zigzag sites on PAH radicals are significantly larger than typical H-abstraction rates. These results are highly relevant in the context of chain reactions of radical species and soot inception under fuel-rich combustion conditions. Furthermore, calculated microcanonical rates that include the additional internal energy released by bond formation (e.g., ring closure to yield C 9 H 9 ) yield significantly higher rates than those associated with full thermalization. These microcanonical considerations are relevant to the astrochemical processes associated with hydrocarbon growth and processing in the low-density interstellar environment.

08 HYDROGEN↗

DOE OSTI2026

Photoenzymatic Csp 3 –Csp 3 bond formation via enzyme-templated radical–radical coupling

Cross-couplings are essential reactions in modern chemical synthesis, enabling the rapid construction of complex molecules from simple precursors. Transition metal catalysts are prized for these transformations because their reactivity and selectivity can be tuned via judicious selection of the metal and ligand. Although enzymes offer analogous opportunities for tuning via protein engineering, their application to cross-coupling remains limited, as nature relies on alternative paradigms for building molecular complexity. Here, we report the cross-coupling of alkyl halides and benzylic carboxylic acids using an engineered flavin-dependent lactate monooxygenase—a photoenzyme. The enzyme achieves this feat by exploiting the redox versatility of the flavin cofactor. Stoichiometric experiments, ultrafast spectroscopy, and computational studies support a mechanism in which photoexcited flavin quinone initiates the reaction via oxidative decarboxylation to generate a benzylic radical. The resulting flavin semiquinone can reduce the alkyl halide to form a second organic radical within the protein active site, which rapidly engages in C(sp 3 )–C(sp 3 ) bond formation. A variant was engineered to control the stereochemical outcome of this radical–radical coupling event, highlighting the ability of the protein to alter the energetic barrier for a mechanistic step that is traditionally understood to be near barrierless. This work demonstrates that the scope for nonnative reaction mechanisms in biocatalysis far exceeds previously established bounds and has potential to solve a variety of reactivity challenges in cross-coupling chemistry.

biocatalysis↗