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At least 847 records · Page 47
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DOE OSTI2025

Fullerene Promotes CO 2 Reduction to Methanol by a Cobalt(II) Phthalocyanine Electrocatalyst

Heterogenization of molecular electrocatalysts offers an attractive way to improve the catalytic selectivity and efficiency of CO 2 conversion to liquid fuels. Herein, we employ density functional theory to compare the mechanism of CO 2 RR by a cobalt(II) tetra(amino)phthalocyanine (Co(II)Pc(NH 2 ) 4 ) electrocatalyst with and without the presence of fullerene support. Our DFT calculations suggest that the CO 2 reduction mechanism is initiated by a metal-based electron reduction followed by subsequent CO 2 nucleophilic addition, electron transfer, proton transfer, water dissociation, and proton-coupled electron transfer steps that lead to CO and methanol formation. We show that graphitic interactions between the Co(II)Pc(NH 2 ) 4 electrocatalyst and C 60 support selectively improve the CO 2 RR to methanol at mild potentials. The undesirable hydrogen evolution reaction (HER) was also investigated for both electrocatalysts and proceeds via the protonation of the cobalt metal center over the nitrogen atom in the inner ring. The competition between the HER and the CO 2 RR was improved in favor of CO and methanol formation using the Co(II)Pc(NH 2 ) 4 @C 60 electrocatalyst. Overall, our results suggest C 60 as a promising graphitic support for molecular electrocatalysts integration for CO 2 catalysis.

Alcohols↗
DOE OSTI2025

Photochemical CO 2 Reduction by a Postsynthetically Modified Zr-MOF

Metal–organic frameworks are an excellent platform for photochemical CO 2 reduction into valuable chemicals. Herein, we report the synthesis and photocatalytic behavior of Ru@MOF-808, a Zr-based MOF, modified with a Ru-polypyridyl complex. The postsynthetic modification was achieved using solvent-assisted incorporation of bipyridine–carboxylate ligands onto the nodes of the MOF-808, followed by the coordination of Ru­(II)-terpyridine moiety. A thorough characterization including 1 H NMR, diffuse reflectance UV/vis, X-ray absorption spectroscopy and gas adsorption studies, combined with DFT calculations, provides strong support for efficient incorporation of the molecular Ru-complex at the loading of one Ru center per node. In the presence of a strong sacrificial reductant BIH, Ru@MOF-808 was found to catalyze the photochemical reduction of CO 2 into a mixture of CO and formate ion. When compared to the homogeneous model catalyst Ru­(tpy)­(bpy) 2+ , Ru@MOF-808 was found to exhibit higher formate yields. Additionally, to explain these formate enhancements, we propose a mechanism that involves CO 2 capture at the MOF nodes to form Zr-bicarbonate species, which further react in a hydride transfer reaction with photogenerated Ru–H donor, thereby outperforming molecular catalysts in HCOO – production. Overall, the results presented in this work indicate the potential of Zr-based MOFs in integrating CO 2 capture with its photochemical conversion to desired products.

CO2 reduction↗
DOE OSTI2025

The [M 6 (S 2 C 2 Ph 2 ) 6 ] (M = Ni, Pd, Pt) Series: Multielectron Reservoirs That Sustain Ligand-Based Oxidations and Metal-Based Reductions

A complete [M 6 (S 2 C 2 R 2 ) 6 ] series (M = Ni (1), Pd (2), Pt (3); R = Ph), the rarest variety among homoleptic dithiolene transition-metal compounds, has been prepared by reaction between [M(S 2 C 2 Ph 2 ) 2 ] and a M 0 source. The platinum member of this set is the first of its type. Diffraction-quality crystals, grown with high reproducibility by evaporation from PhNO 2 solutions, reveal fully reduced [Ph 2 C 2 S 2 ] 2– dianions and an octahedral M 6 core that is reduced to C 2 symmetry by the fusion of a mononuclear D 2h [M(S 2 C 2 Ph 2 ) 2 ] fragment upon a C 4 -symmetric base. The [Ni 6 (S 2 C 2 Ph 2 ) 2 ] 1– monoanion, prepared by Cp* 2 Co reduction, shows only modest structural differences from its neutral counterpart. In CH 2 Cl 2 , 1 and 2 can undergo two reductions and an oxidation, while 3 sustains two reductions and two oxidations. In benzonitrile, 1 sustains three reversible oxidations at potentials that are shifted appreciably to less positive values. The cathodic processes are shown by density functional theory (DFT) calculations to involve an MO largely of metal–sulfur composition that has contributions throughout the C 4 -symmetric pentametallic base of the assembly, while the oxidations are largely ligand-based and confined to the monometallic [M(S 2 C 2 Ph 2 ) 2 ] cap. The absorption spectra are marked by multiple overlapping bands that produce a continuous, tapering absorption profile of unresolved shoulders and swells.

Ligands↗
DOE OSTI2026

How Does Metal Spin State Affect Electronic Communication in Mixed-Valence Dimers? Insights from Ultrafast Near-Infrared and Soft X-ray Transient Absorption Spectroscopy

Recent advancements in photocatalysis, photovoltaics, and quantum information science take advantage of electron spin, and determining how spin multiplicity affects electron transfer is key to understanding these phenomena. Here, in this study, we examine how metal spin state affects electronic communication in an organometallic mixed-valence dimer, ferrocenyl cobaltocenium ([Fe II Cp 2 Co III Cp 2 ] + ). This complex can be photoexcited from its low-spin singlet Fe II ground state to form intermediate-spin triplet Fe II and high-spin quintet Fe II excited states. Using femtosecond optical transient absorption (OTA) spectroscopy with visible (vis), near-infrared (NIR), and short-wave IR (SWIR) probes, supported by time-dependent density functional theory (TD-DFT) calculations, we measure Fe II Co III →Fe III Co II intervalence charge transfer (IVCT) bands in each of the Fe II spin states. Mulliken–Hush analysis of the excited-state IVCT bands was used to compute the electronic coupling between the metal centers in all three spin states, which increased as quintet < triplet < singlet. Meanwhile, the peak energy of the bands, and thus the ΔG of the IVCT transition, increased as triplet < quintet < singlet. Then, to directly probe the electronic structure at each metal center, we employed picosecond soft X-ray transient absorption (XTA) spectroscopy at the Fe and Co L 3 edges. Our results show that the low-spin and high-spin states of [Fe II Cp 2 Co III Cp 2 ] + are valence-localized, while the intermediate-spin state is partially delocalized. The differences in charge delocalization are attributed to differences in orbital occupation and geometry that affect the free energy and superexchange coupling.

Burke, John H. [Univ. of Illinois at Urbana-Champa↗
DOE OSTI2025

Rb 4 CuSb 2 Cl 11 and Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O: Wide Band Gap 0D Metal Halide Semiconductors

Herein, we report the discovery, structural and photophysical characterization of a new zero-dimensional (0D) lead-free all-inorganic halide, Rb 4 CuSb 2 Cl 11 , which adopts a new structure type. Single-crystal X-ray diffraction (SCXRD) shows that the structure consists of isolated, distorted seesaw [SbCl 4 ] − and trigonal planar [CuCl 3 ] 2− units, separated by Rb + cations that provide charge balance. Optoelectronic measurements and density functional theory (DFT) calculations indicate an indirect band gap of 2.89 eV, making it a candidate for wide-bandgap optoelectronic applications. Electrical resistivity was measured at 1.29 × 10 10 Ω·cm, and the trap-state density (n trap ) was found to be 7.44 × 10 10 cm −3 . Attempts to synthesize substitution analogs of Rb 4 CuSb 2 Cl 11 led to the synthesis of Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O, which was erroneously reported as Rb 2 SbCl 5 O in a previous study. Rb 2 In 0.91(0.2) Sb 0.09 Cl 5 ·H 2 O adopts a vacancyordered perovskite structure and exhibits broad-band yellow emission under UV excitation. The measured photoluminescence quantum yield (PLQY) for Rb 2 In 0.91 (0.2)Sb 0.09 Cl 5 ·H 2 O is 18.2%. These findings add to the growing class of quaternary metal halides with multiple cation and anion compositions, expanding the chemical phase space for the discovery of new materials with functional properties.

Crystal structure↗
DOE OSTI2026

Magnetic and EPR Spectroscopic Studies of Thiolate Bridged Divalent Ni, Pd, and Pt Ions Capped with VO(N 2 S 2 ) Metalloligands

Reactions of the metallodithiolate complex VO(bme-dach) (hereafter abbreviated as V, where bme-dach = N,N ′-bis(2-mercaptoethyl)-1,4-diazacycloheptane) with [Pd II (CH 3 CN) 4 ](BF 4 ) 2 and [Pt II (CH 3 CN) 4 ](BF 4 ) 2 yield the V–M–V trimetallic compounds [VPdV](BF 4 ) 2 (2) and [VPtV](BF 4 ) 2 (3). Reaction of a similar metalloligand, VO(bme-daco) (hereafter abbreviated as V′ where bme-daco = N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane) with [Ni II (CH 3 CN) 6 ](BF 4 ) 2 afforded the related salt [V′NiV′](BF 4 ) 2 (1). X-ray structural analyses revealed that cations in 1, 2, and 3 adopt a stairstep C 2h structure consisting of two terminal VO(N 2 S 2 ) moieties bridged via thiolate sulfur to the group 10 metal ions. Weak ferromagnetic superexchange coupling (J = 0.282 cm –1 for 1, 0.954 cm –1 for 2, and 1.372 cm –1 for 3) was observed between the two S = 1/2 V IV centers separated by distances in the range of 5.9–6.3 Å, with J values varying following the order Ni < Pd < Pt. Frozen-solution EPR spectra measured on the more soluble [BArF 24 ] − (BArF 24 – = tetrakis((3,5-trifluoromethyl)phenyl)borate) analogues revealed that the [VPtV] 2+ cation exhibits a 15-line hyperfine splitting of 225 MHz at g = 4 in parallel mode, confirming exchange coupling between the two 51 V, I = 7/2 nuclei. Density-functional theory (DFT) calculations indicate an S = 1 ground state for 1–3. These results demonstrate that the choice of paramagnetic metallodithiolate ligand and diamagnetic bridge in such trimetallic species influences the sign and magnitude of magnetic interactions.

anions↗
DOE OSTI2026

Compositional Tuning of Magnetic Properties in a Series of Transition Metal Site-Deficient UCo x Bi 2 and UNi x Bi 2 Phases

Varying the electronic structure of topological materials through aliovalent substitution is a primary approach to tuning their physical properties. Unlike substitution, metal site deficiency intrinsic to some structure types, including HfCuSi 2 -type, has rarely been employed for controlling the properties of topological phases. In this report, we describe the synthesis and characterization of two new series of compounds, UCoxBi 2 and UNixBi 2 , which demonstrate the variation of transition metal content through synthetic conditions. Magnetic measurements reveal the dependence between the extent of transition metal incorporation and the magnetism of the resulting phase. DFT calculations demonstrated the ability to model their formation and predict the stability ranges of transition metal-site deficient compounds.

Crystal structure↗
DOE OSTI2026

Catalytic Ambient Temperature Dinitrogen Conversion to a Bis(silyl)amine by Mononuclear Group 4 Aryloxide Complexes

The homogeneous conversion of ambient dinitrogen to amine products via the N2 reduction reaction (N2RR) remains a prized yet challenging feat for d-block complexes and is scarcely reported for f-block complexes. New, mononuclear TiIV and ZrIV aryloxide complexes Ti(DP)2 (1Ti), Zr(DP)2 (1Zr), and DP = [2-(OC6H2-2-tBu,4-Me)2CHPh] produce up to 51 eq. and up to 7.0 eq. of HN(SiMe3)2 per Ti/Zr, from N2, K0, weak acid, and chlorotrimethylsilane. Complex 1Ti exhibits more than double the activity toward N2-silylation of any previously reported Ti N2RR catalyst and can also catalyze the formation of up to 19 eq. of NH3, a new feature in early metal N2RR chemistry. The mononuclear 1Zr is the most active Zr catalyst for N2-silylation to date. [KSm(DP)2(THF)3] (1Sm), the mononuclear analogue of our previously reported dinuclear A-Sm complex, displays only stoichiometric N2-silylation due to its vulnerability to deleterious side reactions. DFT calculations confirm the catalysis can proceed via a monomeric Ti complex with a terminally bound, activated N2, agreeing with experimental 1H DOSY NMR measurements; the N-H bond is formed first, directing the catalyst selectivity. The isolable reduction product [K3(THF)Ti(DP)(DP-)(N2)] is also an active catalyst, and an intermediate in the calculated cycle.

Hernandez, Matthew↗
DOE OSTI2026

CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17): Site-Selective Substitution, Electronic Structure, Chemical Bonding, and Structural Transformation

CoSn-type intermetallic compounds have emerged as a model platform for Kagome-derived flat-band physics, where subtle chemical perturbations can strongly influence electronic structure and phase stability. Here, we present a combined experimental and theoretical study of Sb-substitution in CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17) to elucidate the interplay between site selectivity, solubility limit, chemical bonding, and electronic structure. Rietveld refinements on Neutron powder diffraction data confirmed the selective Sb-substitution at the electron-rich In2 (2d) site forming the honeycomb substructure, while the In1 (1a) site within the Kagome layer remains exclusively occupied by In. Density functional theory (DFT) calculations revealed that pristine CoSn-type NiIn hosts Ni 3d-dominated flat bands near the Fermi level (EF), originating from the Kagome-like Ni substructure. Partial replacement of In by Sb within the honeycomb layer alters these flat-band features below EF, reducing the density of states and suppressing the flat-band topology near the Fermi level. Orbital-resolved electronic structure and chemical-bonding analyses show that Sb-substitution enhances Ni-p-block (In/Sb) covalency and optimizes charge compensation, stabilizing the CoSn-type structure up to the solubility limit x ≈ 0.17. Beyond the limit, the higher-Sb compositions show satellite reflections consistent with an incommensurately modulated phase. These results establish a link between site-selective chemical substitution, bonding optimization, and flat-band electronic structure evolution, providing fundamental insights into how chemical substitution influences the electronic properties of Kagome-based intermetallic compounds.

Roy, Nilanjan [National Institute of Technology Si↗
DOE OSTI2026

Iodine Close Packing in Hybrid Halide Bismuth(III) and Antimony(III) Semiconductors: (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10

Simple features in complex hybrid inorganic–organic crystalline materials provide opportunities for targeted discovery of materials with desired optoelectronic properties. In this study, we report the structure and optoelectronic properties of isostructural (NH 3 (CH 2 ) 7 NH 3 ) 2 Bi 2 I 10 and (NH 3 (CH 2 ) 7 NH 3 ) 2 Sb 2 I 10 . The crystal structures are characterized by corner-connected metal-iodide octahedral chains that form a cubic close-packed iodine inorganic framework. Variable temperature UV–visible diffuse reflectance spectroscopy reveals stark contrasts in the onset of absorption and color changes between the [MX6]3– based structures, due to differences in the interaction of the (NH 3 (CH 2 ) 7 NH 3 ) 2+ organic ammonium cation and the iodine packing of the inorganic framework. Density functional theory (DFT) calculations reveal flat bands reflective of the pseudo-1D crystal structure. Dark microwave conductivity (DMC) and time-resolved microwave conductivity (TRMC) reveal an excitonic character with long carrier lifetimes, consistent with the electronically confined octahedral chains. Comparison of the structural features with those of other diammonium-containing crystals reveals that diammoniumheptane can substitute into structures, displacing inorganic octahedra while retaining a close-packed anion framework. This provides a means for targeting new hybrid materials in which “vacancy-ordering” provides a crystal chemical approach for targeting desirable optoelectronic properties.

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

First-Principles Insights into Proton-Coupled Electron Transfer versus Hydrogen Evolution Reaction Selectivity from a Base-Appended Cobaltocene Mediator

Performing selective proton-coupled electron transfer (PCET) to substrates such as N 2 , CO 2 , and unsaturated organic molecules under electrochemical conditions requires the suppression of the competing hydrogen evolution reaction (HER). To address this challenge, our laboratory previously demonstrated a PCET mediator strategy using a dimethylaniline-appended cobaltocene complex, [(CpCoCp NMe2 )H] + , which performs selective reductive chemistry while suppressing the HER. However, the origin of the suppressed, yet still observable, HER has not been thoroughly established. In this work, we perform density functional theory (DFT) calculations to elucidate the HER mechanism involving this redox mediator and to provide atomistic insights into the bifurcation between the PCET and HER pathways. We find that protonation of the aniline moiety to form [CpCoCp NMe2H ] + is more favorable, both kinetically and thermodynamically, than formation of the ring-protonated species [(CpCo(Cp-H) NMe2 )] + . Furthermore, PCET to acetophenone is energetically more favorable via [CpCoCp NMe2H ] + than via [(CpCo(Cp-H) NMe2 )] +1/0 . In contrast, the most favorable HER pathway involves the ring-protonated Co(I) species. These results offer mechanistic insights into HER versus PCET bifurcation and establish guiding principles for designing PCET mediators for selective electroreductive transformations.

evolution reactions↗
DOE OSTI2020

Dehydration of UO 2 Cl 2 ·3H 2 O and Nd(NO 3 ) 3 ·6H 2 O with a Soft Donor Ligand and Comparison of Their Interactions through X-ray Diffraction and Theoretical Investigation [plus Supplemental Information]

Herein we investigated whether the relatively Lewis basic imidazole-2-thiones could be used to substitute water ligands bound to f-element cations and generate f-element soft donor complexes. Reactions of 1,3-diethylimidazole-2-thione (C 2 C 2 ImT) with Nd(NO 3 ) 3 ·6H 2 O and UO 2 Cl 2 ·3H 2 O led to the isolation of the anhydrous thione complexes Nd(NO 3 ) 3 (C 2 C 2 ImT) 3 and UO 2 Cl 2 (C 2 C 2 ImT) 2 , characterized by single crystal X-ray diffraction. Differences in the strength of metal–thione interactions have been examined by means of the crystal structure analysis and density functional theory (DFT) calculations. The C 2 C 2 ImT ligands were found to be affected by both coordination and noncovalent interactions, making it impossible to deconvolute the effects of one from the other. Calculated partial atomic charges indicated greater ligand-to-metal charge transfer in the [UO 2 ] 2+ complex, indicative of a stronger interaction. The reactivity of C 2 C 2 ImT demonstrates its usefulness in the preparation of f-element soft donor complexes from readily available hydrates that could be useful intermediates for promoting the coordination and studying the effects of soft donor anions.

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

A Comprehensive Machine Learning Model for Metal–Ligand Binding Prediction: Applications in Chemistry and Biology

A machine-learning (ML) model that predicts metal–ligand binding constants was developed using the open-source Chemprop software. The model was trained on over 30,000 experimental log K 1 values, which include both protonation and metal–ligand stability constants, comprising over 3500 ligands and 10 2 metal ions from 73 total elements, thus generalizing beyond existing limited approaches, which focus only on specific metals or ligand families. The best-performing model included a combination of SMILES-based molecular representations along with descriptors for the metal ion and experimental conditions. It had an external test R 2 value of 0.942, and MAE value of 0.834. A “SMILES-only” simpler version also produced accurate predictions and preserved the binding trends, serving as a quick and easily accessible alternative for users without computational expertise. The SMILES-only model performed comparably to density functional theory (DFT) calculations but utilized a fraction of the computational resources. The model was successfully applied across diverse domains, including bioinorganic chemistry, heavy metal remediation, and sensor development and demonstrated its effectiveness as a rapid and reliable screening tool for both academic and industrial uses.

Ligands↗
DOE OSTI2020

Reconciling Work Functions and Adsorption Enthalpies for Implicit Solvent Models: A Pt (111)/Water Interface Case Study

Implicit solvent models are a computationally efficient method of representing solid/liquid interfaces prevalent in electrocatalysis, energy storage, and materials science. However, electronic structure changes induced at the metallic surface by the dielectric continuum are not fully understood. To address this, we perform DFT calculations for the Pt(111)/water interface, in order to compare Poisson–Boltzmann continuum solvation methods with ab initio molecular dynamics (AIMD) simulations of explicit solvent. We show that the implicit solvent cavity can be parametrized in terms of the electric dipole moment change at the equilibrated explicit Pt/water interface to obtain the potential of zero charge (PZC). We also compare the accuracy of aqueous enthalpies of adsorption of phenol on Pt(111) using geometry and charge density based dielectric cavitation methods. The ability to parametrize the cavity according to individual atoms, as afforded in the geometry based approach, is key to obtaining accurate enthalpy changes of adsorption under aqueous conditions. Additionally, we show that the electronic structure changes induced by explicit solvent and our proposed implicit solvent parametrization scheme yield comparable density difference profiles and d-band projected density of states. We therefore demonstrate the capability of implicit solvent approaches to capture both the energetics of adsorption processes and the main electronic effects of aqueous solvent on the metallic surface. Therefore, this work provides a scheme for computationally efficient simulations of interfacial processes for applications in areas such as heterogeneous catalysis and electrochemistry.

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

Semi-Automated Creation of Density Functional Tight Binding Models through Leveraging Chebyshev Polynomial-Based Force Fields

Density functional tight binding (DFTB) is an attractive method for accelerated quantum simulations of condensed matter due to its enhanced computational efficiency over standard density functional theory (DFT) approaches. However, DFTB models can be challenging to determine for individual systems of interest, especially for metallic and interfacial systems where different bonding arrangements can lead to significant changes in electronic states. In this regard, we have created a rapid-screening approach for determining systematically improvable DFTB interaction potentials that can yield transferable models for a variety of conditions. Our method leverages a recent reactive molecular dynamics force field where many-body interactions are represented by linear combinations of Chebyshev polynomials. This allows for the efficient creation of multi-center representations with relative ease, requiring only a small investment in initial DFT calculations. Here, we have focused our workflow on TiH 2 as a model system and show that a relatively small training set based on unit-cell-sized calculations yields a model accurate for both bulk and surface properties. Our approach is easy to implement and can yield reliable DFTB models over a broad range of thermodynamic conditions, where physical and chemical properties can be difficult to interrogate directly and there is historically a significant reliance on theoretical approaches for interpretation and validation of experimental results.

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

Even Faster Exact Exchange for Solids via Tensor Hypercontraction

Hybrid density functional theory (DFT) remains intractable for large periodic systems due to the demanding computational cost of exact exchange. We apply the tensor hypercontraction (THC) (or interpolative separable density fitting) approximation to periodic hybrid DFT calculations with Gaussian-type orbitals using the Gaussian plane wave approach. This is done to lower the computational scaling with respect to the number of basis functions (N) and k-points (N k ) at a fixed system size. Additionally, we propose an algorithm to fit only occupied orbital products via THC (i.e., a set of points, N ISDF ) to further reduce computation time and memory usage. This algorithm has linear scaling cost with k-points, no explicit dependence of N ISDF on basis set size, and overall cubic scaling with unit cell size. Significant speedups and reduced memory usage may be obtained for moderately sized k-point meshes, with additional gains for large k-point meshes. Adequate accuracy can be obtained using THC-oo-K for self-consistent calculations. In conclusion, we perform illustrative hybrid density function theory calculations on the benzene crystal in the basis set and thermodynamic limits to highlight the utility of this algorithm.

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

Efficient Parameterization of Density Functional Tight-Binding for 5 f -Elements: A Th–O Case Study

Density functional tight binding (DFTB) models for f-element species are challenging to parametrize owing to the large number of adjustable parameters. The explicit optimization of the terms entering the semiempirical DFTB Hamiltonian related to f orbitals is crucial to generating a reliable parametrization for f-block elements, because they play import roles in bonding interactions. However, since the number of parameters grows quadratically with the number of orbitals, the computational cost for parameter optimization is much more expensive for the f-elements than for the main group elements. In this work we present a set of efficient approaches for mitigating the hurdle imposed by the large size of the parameter space. A novel group-by-orbital correction functions for two-center bond integrals was developed. With this approach the number of parameters is reduced, and it grows linearly with the number of elements, maintaining the accuracy and the number of parameters, in the case of f elements, by more than 40%. The parameter optimization step was accelerated by means of the mini-batch BFGS method. This method allows parameter optimizations with much larger training sets than other single batch methods. A stochastic optimizer was employed that helped overcome shallow local minima in the objective function. The proposed algorithm was used to parametrize the DFTB Hamiltonian for the Th–O system, which was subsequently applied to the study of ThO 2 nanoparticles. The training set consisted of 6322 unique structures, which is barely feasible with conventional optimization methods. The optimized parameter set, LANL-ThO, displays good agreement with DFT-calculated properties such as energies, forces, and structures for both clusters and bulk ThO 2 . Benefiting from the fewer number of parameters and lower computational costs for objective function evaluations, this new approach shows its potential applications in DFTB parametrization for elements with high angular momentum, which present a challenge to conventional methods.

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

Wavelength-Selective Reactivity of Iron(III) Halide Salts in Photocatalytic C–H Functionalization

The utility of halogen radicals in hydrocarbon functionalization extends from early examples of photochemical halogenation to recent reports using photoredox catalysis with iridium complexes and simple transition metal salts such as FeCl 3 . The majority of these methods (uncatalyzed and iron-catalyzed) require UV light (λ ≤ 390 nm), and systematic efforts to enable the use of visible light remain valuable. We report the use of a simple Fe(III) salt that enables a C–H to C–C and C–N functionalization under visible light. The reactivity and selectivity profile using different light sources demonstrates wavelength-selective behavior, which was further investigated with deuterium kinetic isotope effect experiments and DFT calculations. These results show that control over the reactive intermediates in this iron-catalyzed reaction can be achieved through proper choice of the wavelength of irradiation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗