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The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system is currently guided by our understanding of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-enantiomeric excesses of chiral amino acids and sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, remains a key goal of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks on Mars [1-3], NASA’s Curiosity rover has significantly advanced our understanding of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars, if they were present, it is expected that amino acid hydrolysis and racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [4]. One of ESA’s Rosalind Franklin rover payload instruments called the Mars Organic Molecule Analyzer (MOMA) includes a wet chemistry package capable of measuring the enantiomeric ratios of any chiral amino acids present at part-per-million concentrations or higher [5]. The complexity and limited duration of spaceflight operations and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic compounds in ancient rocks make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, and isotopic studies and molecule-specific isotopic and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars comes from biotic or abiotic sources. Ultimately, sample return may be our best chance of identifying chemical biosignatures from a past or present martian biota, if one ever existed on Mars. NASA’s Perseverance rover will collect dozens of surface sample cores for possible future return to Earth by NASA and ESA. Here we review our current knowledge of the distributions and enantiomeric and isotopic compositions of non-biological amino acids found in meteorites compared to terrestrial biochemistry and propose a set of measurement criteria that should be used to help establish the origin of any chiral asymmetry detected in samples from Mars [6].

Daniel P Glavin↗
DOE OSTI2023

Bioinspired Cu(II) Defect Sites in ZIF-8 for Selective Methane Oxidation

Activating the C–H bonds of alkanes without further oxidation to more thermodynamically stable products, CO and CO 2 , is a long-sought goal of catalytic chemistry. Here, inspired by the monocopper active site of methane monooxygenase, we synthesized a Cu-doped ZIF-8 metal–organic framework with 25% Cu and 75% Zn in the nodes and activated it by heating to 200 °C and dosing in a stepwise fashion with O 2 , methane, and steam. We found that it does oxidize methane to methanol and formaldehyde. The catalysis persists through at least five cycles, and beyond the third cycle, the selectivity improves to the extent that no CO 2 can be detected. Experimental characterization and analysis were carried out by PXRD, DRUV–vis, SEM, and XAS (XANES and EXAFS). The reaction is postulated to proceed at open-coordination copper sites generated by defects, and the mechanism of methanol production was explicated by density functional calculations with the revMO6-L exchange–correlation functional. The calculations reveal a catalytic cycle of oxygen-activated Cu I involving the conversion of two molecules of CH 4 to two molecules of CH 3 OH by a sequence of hydrogen atom transfer reactions and rebound steps. For most steps in the cycle, the reaction is more favored by singlet species than by triplets.

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

Tailoring the Coordination Micro‐Environment in Nanotraps for Efficient Platinum/Palladium Separation

Abstract Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high‐tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due to its efficient performance and environmental beingness. However, the challenge lies in effectively recovering and separating individual platinum group metals (PGMs) given their similar chemical properties. Herein, a breakthrough approach is presented by sophisticatedly tailoring the coordination micro‐environment in a series of aminopyridine‐based porous organic polymers, which enables the creation of platinum‐specific nanotraps for efficient separation of binary PGMs (platinum/palladium). The newly synthesized POP‐o2NH 2 ‐Py demonstrates record uptakes and selectivity toward platinum over palladium, with the amino groups adjacent to the pyridine moieties being vital in improving platinum binding performance. Further breakthrough experiments underline its remarkable ability to separate platinum and palladium. Spectroscopic analysis reveals that POP‐o2NH 2 ‐Py offers a more favorable coordination fashion to platinum ions compared to palladium ions owing to the greater interaction between N and Pt 4+ and stronger intramolecular hydrogen bonding between the amino groups and four coordinating chlorines at platinum. These findings underscore the importance of fine‐tuning the coordination micro‐environment of nanotraps through subtle modifications that can greatly enhance the selectivity toward the desired metal ions.

Chemistry↗
DOE OSTI2023

Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole

Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N-donor f-element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz), 5-amino-tetrazole (5-NH 2 -HTetaz), and 1,2,3-triazole (1,2,3-HTriaz) in 1 : 1 and 1 : 3 ratios with CeCl 3 ⋅ 7H 2 O, [C 2 mim] 3 [CeCl 6 ] ([C 2 mim] + =1-ethyl-2-methylimidazolium), and Ce(NO 3 ) 3 ⋅ 6H 2 O. Although unsuccessful in our goal, structural analysis revealed that neutral 4-NH 2 -1,2,4-Triaz is structure directing via η 2 μ 2 κ 2 bridging, with the formation of the dinuclear complexes [Ce 2 Cl 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (H 2 O) 8 ]Cl 4 ⋅ 4H 2 O, [Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (4-NH 2 -1,2,4-Triaz) 2 (Cl) 6 ], and [4-NH 2 -1,2,4-HTriaz][Ce 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 2 (μ 2 -NO 3 )(NO 3 ) 6 (H 2 O) 2 ]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 2 (μ 3 -Cl) 2 (Cl) 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 12 ] ⋅ 7H 2 O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N-donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non-oxo coordinating anions in the M 6 X 8 core, and the first reported Ce(III) hexanuclear complex of this type.

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

Atomically Dispersed Single Ni Site Catalysts for Nitrogen Reduction toward Electrochemical Ammonia Synthesis Using N 2 and H 2 O

Ammonia (NH 3 ) electrosynthesis gains significant attention as NH 3 is essentially important for fertilizer production and fuel utilization. However, electrochemical nitrogen reduction reaction (NRR) remains a great challenge because of low activity and poor selectivity. Herein, a new class of atomically dispersed Ni site electrocatalyst is reported, which exhibits the optimal NH 3 yield of 115 µg cm -2 h -1 at –0.8 V versus reversible hydrogen electrode (RHE) under neutral conditions. High faradic efficiency of 21 ± 1.9% is achieved at -0.2 V versus RHE under alkaline conditions, although the ammonia yield is lower. The Ni sites are stabilized with nitrogen, which is verified by advanced X-ray absorption spectroscopy and electron microscopy. Density functional theory calculations provide insightful understanding on the possible structure of active sites, relevant reaction pathways, and confirm that the Ni-N 3 sites are responsible for the experimentally observed activity and selectivity. Extensive controls strongly suggest that the atomically dispersed NiN 3 site-rich catalyst provides more intrinsically active sites than those in N-doped carbon, instead of possible environmental contamination. Overall, this work further indicates that single-metal site catalysts with optimal nitrogen coordination is very promising for NRR and indeed improves the scaling relationship of transition metals.

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

The carboxylation status of osteocalcin has important consequences for its structure and dynamics

The carboxylation status of Osteocalcin (Ocn) not only influences formation and structure in bones but also has important endocrine functions affecting energy metabolism and expenditure. In this study, the role of γ-carboxylation of the glutamate residues in the structure-dynamics-function relationship in Ocn is investigated. Three forms of Ocn, differentially carboxylated at the Glu-17, 21 and 24 residues, along with a mutated form of Ocn carrying Glu/Ala mutations, are modeled and simulated using molecular dynamics (MD) simulation in the presence of calcium ions. Characterization of the global conformational dynamics of Ocn, described in terms of the orientational variations within its 3-helical domain, highlights large structural variations in the non-carboxylated osteocalcin (nOcn). The bi-carboxylated Ocn (bOcn) and tri-carboxylated (tOcn) species, in contrast, display relatively rigid tertiary structures, with the dynamics of most regions strongly correlated. Radial distribution functions calculated for both bOcn and tOcn show long-range ordering of the calcium ion distribution around the carboxylated glutamate (γGlu) residues, likely playing an important role in promoting stability of these Ocns. Additionally, the same calcium ions are observed to coordinate with neighboring γGlu, better shielding their negative charges and in turn stabilizing these systems more than do the singly coordinating calcium ions observed in the case of nOcn. bOcn is also found to exhibit a more helical C-terminal structure, that has been shown to activate its cellular receptor GPRC6A, highlighting the allosteric role of Ocn carboxylation in modulating the stability and binding potential of the active C-terminal. Furthermore, the carboxylation status of Ocn as well and its calcium coordination appear to have a direct influence on Ocn structure and dynamics, possibly leading to the known differences in Ocn biological function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Changes in nitrate binding with lanthanides in BLPhen complexes

Preorganized ligands such as bis-lactam-1,10-phenanthroline (BLPhen) offer unique selectivity trends in solvent extraction of rare-earth ions, particularly from aqueous nitrate solutions. However, due to the ligand’s lipophilicity it is experimentally challenging to obtain crystal structures of the corresponding lanthanide (Ln):ligand complexes to describe the local structure of the first coordination shell and the role of the nitrate ions in the organic phase. In this work, we report first principles molecular dynamics (FPMD) simulations of the complexation of trivalent lanthanide ions (La, Nd, and Eu) with the BLPhen ligand in the presence of nitrate ions in the dichloroethane (DCE) solvent. We find that two nitrate anions are present in the first solvation shell and the third nitrate anion is far from the first solvation shell in all three [Ln(BLPhen) 2 ] 3+ complexes examined. Moving along the lanthanide series from La to Nd to Eu, the binding pocket formed by the two BLPhen ligands shrinks in size; as a result, the two nitrate configuration changes from one-monodentate/one-bidentate binding mode for La and Nd to all monodentate for Eu. Meanwhile, the total coordination number drops from 11 for La and Nd to 10 for Eu. More interestingly, the bidentate binding in [La(BLPhen) 2 ] 3+ and [Nd(BLPhen) 2 ] 3+ complexes is highly dynamic, frequently switching to monodentate and back. The FPMD insights into the differing modes and dynamics of nitrates in the first coordination shell will be useful for further atomistic understanding of the complex structure, formation, and stability in the organic phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Quantifying the Relevance of Long-Range Forces for Crystal Nucleation in Water

Understanding nucleation from aqueous solutions is of fundamental importance in a multitude of fields, ranging from materials science to biophysics. The complex solvent-mediated interactions in aqueous solutions hamper the development of a simple physical picture, elucidating the roles of different interactions in nucleation processes. In this study, we make use of three complementary techniques to disentangle the role played by short- and long-range interactions in solvent-mediated nucleation. Specifically, the first approach we utilize is the local molecular field (LMF) theory to renormalize long-range Coulomb electrostatics. Second, we use well-tempered metadynamics to speed up rare events governed by short-range interactions. Third, the deep learning-based State Predictive Information Bottleneck approach is employed in analyzing the reaction coordinate of the nucleation processes obtained from the LMF treatment coupled with well-tempered metadynamics. We find that the two-step nucleation mechanism can largely be captured by the short-range interactions, while the long-range interactions further contribute to the stability of the primary crystal state under ambient conditions. Furthermore, by analyzing the reaction coordinate obtained from the combined LMF-metadynamics treatment, we discern the fluctuations on different time scales, highlighting the need for long-range interactions when accounting for metastability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Reactivity and Mechanisms of Methane, Ethane, and Benzene C–H Amination with an Iodine(III) Bistriflimide Complex

The iodine(III) bistriflamide complex (C 6 F 5 ) III I(NTf 2 ) 2 in HNTf 2 (bistriflimide acid; (CF 3 SO 2 ) 2 NH) selectively aminates methane and ethane. At a 100 °C reaction with methane after 3 h, it resulted in the exclusive formation of MeNTf 2 with a yield of approximately 40%. For ethane, at 100 °C in 2 h, a > 80% yield was found for a combination of monofunctionalized and difunctionalized amination products. In contrast to alkanes giving functionalized products, the reaction of (C 6 F 5 ) III I(NTf 2 ) 2 with benzene resulted in being stalled at (C 6 F 5 )I III (Ph)(NTf 2 ) with a <5% conversion to PhNTf 2 even at 120 °C. PWPB95-D3(BJ) density functional theory calculations indicate that C–H activation is the lowest energy pathway to break the hydrocarbon bonds and is lower in energy than radical, electron-transfer, proton-coupled electron-transfer, or hydride substitution pathways. For methane, from the (C 6 F 5 )I III (CH 3 )(NTf 2 ) intermediate, there is a one-step amine functionalization mechanism that avoids a carbocation intermediate. For ethane, from the (C 6 F 5 )I III (Et)(NTf 2 ) intermediate, dynamics simulations suggest the possibility of a competitive two-step functionalization pathway that involves a short-lived carbocation intermediate. As a result, a reaction coordinate strain analysis provides a straightforward model for understanding the relative reactivity rates for alkyl versus aryl functionalization.

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

Probing Terra Incognita of Ni–P Catalysts: Operando Explorations during Hydrogen Evolution Reaction

We have developed two Ni phosphide preparation methods allowing operando XAS surface-sensitive studies of well-defined bulk systems. For Ni K-edge XAS, a Ni 2 P phase-pure powder was sintered into a high-density pellet and polished for grazing incidence XAS. Ni sites were mildly affected by the acidic electrolyte prior to the HER, while the applied cathodic potential caused the reduction of Ni surface states beyond the states of as-prepared Ni 2 P. The computed fully H-covered Ni 2 P [0001] model describes the difference in the operando Ni K-edge GIXAS spectrum well. Upon turning the applied bias off, the Ni sites became immediately oxidized, forming NiO on the surface. Thus, the active phase during the HER is covalent Ni 0 close to that in the intermetallic phosphides, and Ni 2+ oxides formed after, and not during, the HER. For P K-edge XAS, Ni foam was phosphorized to form a thin Ni 3 P layer while preserving its high surface area. Upon immersion in the acidic electrolyte, the P sites underwent removal of P 5+ phosphates and formed new P coordination, possibly due to the adsorption of protons from the electrolyte. These new P surface states were not affected by turning the cathodic current on and off as soon as the sample was immersed in the acidic electrolyte. However, the removal of the sample from the electrochemical cell and drying in air resulted in substantial depletion and oxidation of surface P. Echoing the observed Ni site chemistry during HER, XAS and XPS suggest that the in situ active P sites are different from the oxidized P states observed under ex situ conditions.

Kong, Seongyoung [Iowa State Univ., Ames, IA (Unit↗
DOE OSTI2026

Ultrafast solvent-to-solute proton transfer mediated by intermolecular coherent vibrations

Ultrafast photoinduced excited-state proton transfer (ESPT) plays a crucial role in protecting biomolecules and functional materials from photodamage. However, the influence of solute-solvent interactions on ESPT dynamics remains under active investigation. Here, we present an ultrafast spectroscopic study of ESPT in the photobase 2-(2´-pyridyl)benzimidazole (PBI) in methanol. Ultrafast absorption spectroscopy, supported by quantum chemical calculations, reveals three distinct kinetic steps: (1) a 2.2 ps solvent-to-solute proton transfer, (2) subsequent nonradiative relaxation to the ground state within 31 ps, producing a vibrationally hot ensemble with substantial excess kinetic energy, and (3) equilibration as this energy dissipates into the surrounding solvent bath over 186 ps. Femtosecond-resolved dynamics exhibit oscillatory signals indicative of coherent wavepacket motion on the S 1 potential energy surface. A phase flip in the excited-state absorption maximum confirms this assignment. Fourier analysis resolves two dominant periods (∼117 fs and ∼340 fs), corresponding to in-plane and out-of-plane vibrational modes coupled between PBI and the hydrogen-bonded methanol molecule. The rapid dephasing ( < 300 fs) suggests that the nuclear wavefunction evolves on an anharmonic potential energy surface while traversing the ESPT reaction coordinate.

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

Full 3D Kinetic Modeling and Quantification of Positive Streamer Evolution in an Azimuthally Swept Pin-to-Plane Wedge Geometry

Cathode-directed streamer evolution in near atmospheric air is modeled in 3D pin-to-plane geometries using a 3D kinetic Particle-In-Cell (PIC) code that simulates particle-particle collisions via the Direct Simulation Monte Carlo (DSMC) method. Due to the computational challenges associated with a complete 360° volumetric domain, a practical alternative was achieved using a wedge domain and a range of azimuthal angles was explored (5°, 15°, 30°, and 45°) to study possible effects on the streamer growth and propagation due to the finite wedge angle. A DC voltage of 6 kV is administered to a hemispherical anode of radius 100 μm, with a planar cathode held at ground potential, generating an over-volted state with an electric field of 4 MV/m across a 1500 μm gap. The domain is seeded with an initial ion and electron density of 10 18 m -3 at 1 eV temperature confined to a spherical region of radius 100 μm centered at the tip of the anode. The air chemistry model [1] includes standard Townsend breakdown mechanisms (electron-neutral elastic, excitation, ionization, attachment, and detachment collision chemistry and secondary electron emission) as well as streamer mechanisms (photoionization and ion-neutral collisions) via tracking excited state neutrals which can then either quench via collisions or spontaneously emit a photon based on specific Einstein-A coefficients [2, 3]. In this work, positive streamer dynamics are formally quantified for each wedge angle in terms of electron velocity and density as temporal functions of coordinates r, Φ, and z. Applying a random plasma seed for each simulation, particles of interest are tracked with near femtosecond temporal resolution out to 1.4 ns and spatially binned. This process is repeated six times and results are averaged. Prior 2D studies have shown that the reduced electric field, E/n, can significantly impact streamer evolution [4]. We extend the analysis to 3D wedge geometries, to limit computational costs, and examine the wedge angle’s effect on streamer branching, propagation, and velocity. Results indicate that the smallest wedge angle that produced an acceptably converged solution is 30°. The potential effects that a mesh, when under-resolved with respect to the Debye length, can impart on streamer dynamics and numerical heating were not investigated, and we explicitly state here that the smallest cell size was approximately 10 times the minimum λ D in the streamer channel at late times. This constraint on cell size was the result of computational limitations on total mesh count.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1984

North-south asymmetries of solar particle events in upper stratospheric ozone

Stratospheric ozone depressions, following intense solar particle events (SPE) observed by the backscattered ultraviolet (BUV) experiment on the Nimbus-4 satellite, indicate the existence of distinct asymmetries between the Northern and Southern Hemispheres. These asymmetries are observed in the magnitude of the depressions above the 5-mb level, their temporal variations, and the spatial (i.e., latitude and longitude) dependence of these variations. Possible causes of asymmetries, shown by two events on August 4, 1972 and January 25, 1971, can be attributed to: (1) tilt of the interplanetary magnetic field (IMF) with respect to the earth's dipole magnetic field which influences the precipitation of energetic solar particles into the polar atmospheres; (2) differences in ozone chemistry caused by the large change in atmospheric temperature between summer and winter hemispheres; (3) seasonal differences of the stratosphere's dynamic states which are affected by upward propagating planetary waves in winter in contrast to the relatively undisturbed zonal flows in summer; and (4) topographic asymmetry between Northern and Southern Hemispheres. These effects are shown by three-dimensional plots of the events in geographic coordinates and by color contour plots of the stratospheric ozone distributions in geomagnetic and geographic polar coordinates, respectively.

Maeda, K.↗
DOE OSTI2022

Understanding Proton Movement in [Fe-Fe] Hydrogenases

Nature uses specialized metalloenzymes to carry out small molecule activation reactions, including CO 2 fixation, O 2 activation, and proton reduction, with unparalleled efficiency, rates, and selectivity. The latter reactions are performed by hydrogenases, protein metallo-complexes that interconverts H 2 to protons and electrons (H 2 oxidation) and the reverse reaction (H 2 production) with incredibly low energy input and amazingly fast kinetics. Reproducing both the activity and efficiency of metalloenzymes in sustainable anthropogenic systems remains one of the “holy grails” of inorganic chemistry. However, identifying the precise molecular components responsible for these desirable properties has been challenging in the natural metalloenzymes, hindering efforts to develop analogous processes in synthetic compounds. Considering the inherent complexity of a metalloenzyme and the many interactions, both strong and weak, that contribute to the function of an enzyme, we have elected to model natural metalloenzymes on a biochemical platform. Towards this end, we have a developed structural, functional, and mechanistic mimic of the [Ni-Fe] hydrogenases within a robust protein scaffold, rubredoxin, to understand the influence of the secondary coordination environment on the metal center. This involved preparing a series of three rubredoxin constructs containing a single point mutation at Val positions and making the NMR chemical shift assignments for the paramagnetic (nickel-substituted) and non-paramagnetic (zinc-substituted) form. These physical studies were complemented with in silico molecular dynamic studies on proteins with [Fe-S] clusters to engineer new proton channels to test in vitro . To assist our search for new natural metalloprotein scaffolds within the vast number of sequenced genomes, we created a neural network-based program to identify proteins with specific metal-binding sites. These computational and physical studies with metalloenzymes provide direct insight into the fundamental chemical principles driving the natural systems and offer design principles for developing catalysts that utilize analogous principles.

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

Investigating trends in actinide covalency and magnetism with 35/37 Cl SSNMR spectroscopy and first-principles calculations

Solid-state NMR (SSNMR) spectroscopy is a powerful technique for studying actinide chemistry but has been significantly limited due to the complex paramagnetism, and radiological hazards presented by these materials. Lanthanide and actinide salts often feature magnetic ordering and can be paramagnetic, ferromagnetic, or antiferromagnetic depending on temperature and electronic structure. Paramagnetic interactions can manifest in SSNMR both as secular spectral shifts and/or couplings as well as contributions from non-secular relaxation. Both effects can be directly measured with NMR and used to extrapolate rich chemical information such as coordination environments, bonding characteristics, local molecular dynamics, and correlation times. Typically, these studies are carried out on high-γ and highly abundant NMR-active isotopes (e.g., 1 H, 6/7 Li, 19 F, 23 Na, etc.) or on enriched rare isotopes (e.g., 2 H and 17 O), which can be expensive. Herein, we present a facile methodology to measure the 35/37 Cl electric-field gradient (EFG) and paramagnetic shift anisotropy (SA) tensor components using static wideline SSNMR measurements of LaCl 3 , NdCl 3 , UCl 3 , and UCl 4 . The static powder spectra were measured with both 35 Cl and 37 Cl SSNMR to increase the fidelity of the extracted tensor parameters. Variable temperature NMR of a select case confirms the Curie–Weiss paramagnetism. Relaxation measurements of both nuclei further corroborate observations owing to the paramagnetic relaxation enhancement and reveal simultaneous quadrupolar relaxation mechanisms. Density functional theory (DFT) calculations using Hubbard U corrections to the uranium valence orbitals show excellent agreement with experimental EFG tensor parameters and help describe the bonding characteristics in these lanthanide and actinide systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Revisiting the Bonding Model for Gold(I) Species: The Importance of Pauli Repulsion Revealed in a Gold(I)–Cyclobutadiene Complex

Understanding the bonding of gold(I) species has been central to the development of gold(I) catalysis. Herein, we present the synthesis and characterization of the first gold(I)-cyclobutadiene complex, accompanied with bonding analysis by state-of-the-art energy decomposition analysis methods. Analysis of possible coordination modes for the new species not only confirms established characteristics of gold(I) bonding, but also suggests that Pauli repulsion is a key yet hitherto overlooked element. Additionally, we obtain a new perspective on gold(I)-bonding by comparison of the gold(I)-cyclobutadiene to congeners stabilized by p-, d-, and f-block metals. Consequently, we refine the gold(I) bonding model, with a delicate interplay of Pauli repulsion and charge transfer as the key driving force for various coordination motifs. Finally, Pauli repulsion is similarly determined as a significant interaction in Au I -alkyne species, corroborating this revised understanding of Au I bonding.

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

CO 2 Chemisorption Behavior of Coordination-Derived Phenolate Sorbents

CO 2 chemisorption via C-O bond formation is an efficient methodology in carbon capture especially using phenolate-based ionic liquids (ILs) as the sorbents to afford carbonate products. However, most of the current IL systems involve alkylphosphonium cations, leading to side reactions via the ylide intermediate pathway. It is important to figure out the CO 2 chemisorption behavior of phenolate-derived sorbents using inactive and easily accessible cation counterparts without active protons. Herein, phenolate-based systems were constructed via coordination between alkali metal cations with crown ethers to avoid the participation of active protons in CO 2 chemisorption. Reaction pathway study revealed that CO 2 uptake could be achieved by O-C bond formation to afford carbonate. CO 2 uptake capacity and reaction enthalpy were significantly influenced by the coordination effect, alkali metal types, and alkyl groups on the benzene ring.

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

Simulation studies of polypeptoids using replica exchange with dynamical scaling and dihedral biasing

Polypeptoids differ from polypeptides in that the amide bond can more frequently adopt both cis and trans conformations. The transition between the two conformations requires overcoming a large energy barrier, making it difficult for conventional molecular simulations to adequately visit the cis and trans structures. A replica-exchange method is presented that allows for easy rotations of the amide bond and also an efficient linking to a high temperature replica. The method allows for just three replicas (one at the temperature and Hamiltonian of interest, a second high temperature replica with a biased dihedral potential, and a third connecting them) to overcome the amide bond sampling problem and also enhance sampling for other coordinates. Here our results indicate that for short peptoid oligomers, the conformations can range from all cis to all trans with an average cis/trans ratio that depends on side chain and potential model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗