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At least 883 records · Page 49
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DOE OSTI2021

Influence of diluent concentration in localized high concentration electrolytes: elucidation of hidden diluent-Li + interactions and Li + transport mechanism

Localized high concentration electrolytes (LHCE) offer a viable dilution strategy for high concentration electrolytes (HCE) as the dilution process barely impacts the enhanced reductive/oxidative behavior of the HCE formulation but significantly lowers the overall viscosity and, in most cases, increases the ionic conductivity. On the other hand, experimental studies indicate that fluorinated ether electrolytes such as 1,1,2,2-tetrafluoroethylene 2,2,3,3-tetrafluoropropyl ether (TTE) help grow enhanced passivation layers on Ni-rich NMC cathodes. In this work, we study LHCE formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethyl carbonate (DMC), and TTE as the diluent. Here we use molecular dynamics methodologies, and Raman spectra measurements, to address to what extent the diluent content impacts the coordination behavior of the aggregated structures in the electrolyte and to evaluate the Li + transport properties under the influence of an external electric field. In contrast to other fluorinated ethers, we find that TTE interacts with Li + via fluorine atoms, partially limiting the DMC–Li + interactions hence altering the Li + solvation coordination. This competitive interaction with Li+ between the organic solvent and the TTE diluent influences the electrolyte's reductive/oxidative behavior. Nevertheless, the bonding strength of the Li + –F TTE is much weaker than those of the Li + –O DMC and Li + –OFSI – . Therefore, the existence of Li + –F TTE is in a transient state rather than in a steady state. These results provide plausible guiding rules for future dilution strategies of HCE electrolytes. We also demonstrate that Li + ions drift under the electric field's influence via repeated ion dissociation/association processes following a hopping conduction mechanism. Li + ions jump between aggregated networks where Li–O interactions dominate via diluent-enriched phases, a process in which the solvation shells temporarily mutate to a Li–F dominated coordination structure. We expect our results to contribute an improved atomic-level understanding of the solvation structure and dynamics of LHCE electrolytes.

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

An extensive assessment of the performance of pairwise and many-body interaction potentials in reproducing ab initio benchmark binding energies for water clusters n = 2–25

We assess the performance of 7 pairwise additive (TIP3P, TIP4P, TIP4P-ice, TIP5P, OPC, SPC, SPC/E) and 8 families of many-body potentials (q-AQUA, HIPPO, AMOEBA, EFP, TTM, WHBB, MB-pol, MB-UCB) in reproducing high-level ab initio benchmark values, CCSD(T) or MP2 at the complete basis set (CBS) limit for the binding energy and the many-body expansion (MBE) of water clusters n = 2–11, 16–17, 20, 25. By including a large range of cluster sizes having dissimilar hydrogen bonding networks, we obtain an understanding of how these potentials perform for different hydrogen bonding arrangements that are mostly outside of their parameterization range. While it is appropriate to compare the results of ab initio based many-body potentials directly to the electronic binding energies (D e 's), the pairwise additive ones are compared to the enthalpies at T = 298 K, ΔH(298 K), as the latter class of force fields are parametrized to reproduce enthalpies (implicitly accounting for zero-point energy corrections) rather than binding energies. We find that all pairwise additive potentials considered overestimate the reference ΔH values for the n = 2–25 clusters by >13%. For the water dimer (n = 2) in particular, the errors are in the range 83–119% for the pairwise additive potentials studied since these are based on an effective rather than the true 2-body interaction specifically designed as a means of partially accounting for the missing many-body terms. This stronger 2-body interaction is achieved by an enhanced monomer dipole moment that mimics its increase from the gas phase monomer to the condensed phase value. Indeed, for cluster sizes n ≥ 4 the percent deviations become slightly smaller (albeit all exceeding 13%). In contrast, we find that the many-body potentials perform more accurately in reproducing the electronic binding energies (D e 's) throughout the entire cluster range (n = 2–25), all reproducing the ab initio benchmark binding energies within ±7% of the respective CBS values. We further assess the ability of a subset of the many-body potentials (MB-UCB, q-AQUA, MB-pol, and TTM2.1-F) to also reproduce the magnitude of the ab initio many-body energy terms for water cluster sizes n = 7, 10, 16 and 17. The potentials show an overall good agreement with the available benchmark values. However, we identify characteristic differences upon comparing the many-body terms at both the ab initio-optimized geometries and the respective potential-optimized geometries to the reference ab initio values. Additionally, by applying this analysis to a wide range of cluster sizes, trends in the MBE of the potentials with increasing cluster size can be identified. Finally, in an attempt to draw a parallel between the pairwise additive and many-body potentials, we report the analysis of the individual molecular dipole moments for water clusters with 1 to ~4 solvation shells with the TTM2.1-F potential. We find that the internally solvated water molecules have in general a larger molecular dipole moment ranging from 2.6–3.0 D. This justifies the use of an enhanced, with respect to the gas-phase value, molecular dipole moment for the pairwise additive potentials, which is intended to fold in the many body terms into an effective (enhanced) pairwise interaction through the choice of the charges. These results have important implications for the development of future generations of efficient, transferable, and highly accurate classical interaction potentials in both the pairwise additive and many-body categories.

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

A critical comparison of CH∙∙∙π versus π∙∙∙π interactions in the benzene dimer: obtaining benchmarks at the CCSD(T) level and assessing the accuracy of lower scaling methods

In this study, we have established CCSD(T)/CBS (Complete Basis Set) limits for 3 stationary points on the benzene dimer potential energy surface, corresponding to the π∙∙∙π (parallel displaced or PD(C 2h ), minimum) and CH∙∙∙π (T-shaped or T(C 2v ), transition state) and tilted T-shaped (or TT(Cs), minimum) bonding scenarios considering both the structure and binding energy. The CCSD(T)/CBS binding energies are -2.65 ± 0.02 (PD), -2.74 ± 0.03 (T), and -2.83 ± 0.01 kcal mol -1 (TT). To this end, the CH∙∙∙π is ~0.2 kcal mol -1 stronger than the π∙∙∙π interaction, whereas the tilting of the CH donating benzene molecule with respect to the other benzene is worth 0.1 kcal mol -1 . As previously discussed in the literature, the MP2 level of theory does not provide a close match for either the energy or structure, yet the SCS-MP2 yields structures in excellent agreement with respect to the CCSD(T) result. It is found that the SCS-MI-MP2 also gives optimized structures very close to SCS-MP2 (within ~0.01 Å of the benchmark). Despite the closer match in structure, the spin-biased MP2 methods (SCS-, SCS-MI-, and SOS-MP2) incorrectly predict the relative stabilities of the isomers. That said, none of the spin biased MP2 methods offers a good compromise between energy and structure for the systems examined. Finally, the CCSD(T)/CBS benchmarks were used to assess the performance of 13 DFT functionals selected from different rungs of Jacob's ladder. Several functionals such as TPSS-D3, B3LYP-D3, B97-D, B97-D3, and B2PLYP-D3 provided a good description of the binding energies for both CH∙∙∙π and π∙∙∙π interactions, yielding values within 6% of the CCSD(T)/CBS benchmark values. Unlike the MP2 methods, these functionals correctly predict the relative stability of the PD(C 2h ) and T(C 2v ) dimers. Further, we find that there is no systematic improvement as Jacob's ladder is ascended (increased complexity of functional). The best functionals that result in a good compromise between structure and energy accuracy are B97-D3 and B2PLYP-D3 for both the CH∙∙∙π and π∙∙∙π interaction. Despite the impressive performance of these functionals, a challenge that remains is ensuring the transferability of these density functionals in accurately describing the interaction between dimers of larger aromatic molecules, the latter requiring high-level benchmarks for these systems.

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

Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis

Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (i.e., support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal–support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called “strong metal–support interactions” have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.

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

Investigating PVC polymer–plasticizer interactions with atomistic MD simulations and potential of mean force calculations

For this work, atomistic molecular dynamics (MD) simulations coupled with potential of mean force (PMF) calculations were employed to investigate the interactions between PVC polymer chains containing 6–20 repeating units and various plasticizers, with the goal of identifying potential replacements for the toxic plasticizer di(2-ethylhexyl)phthalate (DEHP) used in blood bags. The selected plasticizers belong to various chemical families, such as orthophthalates, citrates, adipates, and the terephthalate DEHT. Both the polymer and the plasticizers lack ionizable groups, and their interactions are primarily governed by van der Waals and electrostatic forces. A model correlating PMF profiles with interaction forces was developed and validated across polyvinyl chloride (PVC) polymers of different lengths and all investigated plasticizers. This model provides insight into how structural variations in plasticizers influence their respective PMF values. The study ranks the investigated plasticizers based on binding affinity, identifying TOTM (tris(2-ethylhexyl) trimellitate, TEHTM), BTHC (butyryl trihexyl citrate, Citroflex B-6), ATHC (acetyl trihexyl citrate, Citroflex A-6, CA-6), and DEHT (bis(2-ethylhexyl)terephthalate, DOTP/DEHTP) as promising alternatives for further investigation. This comprehensive study encompasses PVC polymers of four different lengths and 14 plasticizers, with all data averaged over 30 independent simulations. The approach provides a deeper understanding of molecular interactions, enabling the tailoring of polymer–plasticizer systems for diverse applications, including extractables and leachables, with relevance spanning materials science to biomedical engineering, and also serves as a basis for developing coarse-grained simulation protocols. Overall, this study provides valuable insights for designing safer and more efficient plasticizer substitutes and is well supported by other studies.

Shet, Sai Athmeeya G. [Sri Sathya Sai Institute of↗
DOE OSTI2025

Harnessing peptide–cellulose interactions to tailor the performance of self-assembled, injectable hydrogels

Taking inspiration from natural systems, such as spider silk and mollusk nacre, that employ hierarchical assembly to attain robust material performance, we leveraged matrix–filler interactions within reinforced polymer–peptide hybrids to create self-assembled hydrogels with enhanced properties. Specifically, cellulose nanocrystals (CNCs) were incorporated into peptide–polyurea (PPU) hybrid matrices to tailor key hydrogel features through matrix–filler interactions. Herein, we examined the impact of peptide repeat length and CNC loading on hydrogelation, morphology, mechanics, and thermal behavior of PPU/CNC composite hydrogels. The addition of CNCs into PPU hydrogels resulted in increased gel stiffness; however, the extent of reinforcement of the nanocomposite gels upon nanofiller inclusion also was driven by PPU architecture. Temperature-promoted stiffening transitions observed in nanocomposite PPU hydrogels were dictated by peptide segment length. Analysis of the peptide secondary structure confirmed shifts in the conformation of peptidic domains (α-helices or β-sheets) upon CNC loading. Finally, PPU/CNC hydrogels were probed for their injectability characteristics, demonstrating that nanofiller–matrix interactions were shown to aid rapid network reformation (∼10 s) upon cessation of high shear forces. Overall, this research showcases the potential of modulating matrix–filler interactions within PPU/CNC hydrogels through strategic system design, enabling the tuning of functional hydrogel characteristics for diverse applications.

42 ENGINEERING↗
DOE OSTI2024

Numerical challenges for energy conservation in N -body simulations of collapsing self-interacting dark matter halos

Dark matter (DM) halos can be subject to gravothermal collapse if the DM is not collisionless, but engaged in strong self-interactions instead. When the scattering is able to efficiently transfer heat from the centre to the outskirts, the central region of the halo collapses and reaches densities much higher than those for collisionless DM. This phenomenon is potentially observable in studies of strong lensing. Current theoretical efforts are motivated by observations of surprisingly dense substructures. However, a comparison with observations requires accurate predictions. One method to obtain such predictions is to use N-body simulations. Collapsed halos are extreme systems that pose severe challenges when applying state-of-the-art codes to model self-interacting dark matter (SIDM). In this work, we investigate the root of such problems, with a focus on energy non-conservation. Moreover, we discuss possible strategies to avoid them. We ran N-body simulations, both with and without SIDM, of an isolated DM-only halo and we adjusted the numerical parameters to check the accuracy of the simulation. We find that not only the numerical scheme for SIDM can lead to energy non-conservation, but also the modelling of gravitational interaction and the time integration are problematic. The main issues we find are: (a) particles changing their time step in a non-time-reversible manner; (b) the asymmetry in the tree-based gravitational force evaluation; and (c) SIDM velocity kicks breaking the time symmetry. Tuning the parameters of the simulation to achieve a high level of accuracy allows us to conserve energy not only at early stages of the evolution, but also later on. However, the cost of the simulations becomes prohibitively large as a result. Some of the problems that make the simulations of the gravothermal collapse phase inaccurate can be overcome by choosing appropriate numerical schemes. However, other issues still pose a challenge. Our findings motivate further works on addressing the challenges in simulating strong DM self-interactions.

dark matter↗
DOE OSTI2020

The Fermi–Löwdin self-interaction correction for ionization energies of organic molecules

(Semi)-local density functional approximations (DFAs) suffer from self-interaction error (SIE). When the first ionization energy (IE) is computed as the negative of the highest occupied orbital (HO) eigenvalue, DFAs notoriously underestimate them compared to quasi-particle calculations. Here, the inaccuracy for the HO is attributed to SIE inherent in DFAs. We assessed the IE based on Perdew-Zunger self-interaction correction on 14 small to moderate-sized organic molecules relevant in organic electronics and polymer donor materials. Though self-interaction corrected DFAs were found to significantly improve the IE relative to the uncorrected DFAs, they overestimate. However, when the self-interaction correction is interiorly scaled using a function of the iso-orbital indicator zs , only the regions where SIE is significant get a correction. We discuss these approaches and show how these methods significantly improve the description of the HO eigenvalue for the organic molecules.

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

Exploring and enhancing the accuracy of interior-scaled Perdew–Zunger self-interaction correction

The Perdew–Zunger self-interaction correction (PZ-SIC) improves the performance of density functional approximations for the properties that involve significant self-interaction error (SIE), as in stretched bond situations, but overcorrects for equilibrium properties where SIE is insignificant. This overcorrection is often reduced by local scaling self-interaction correction (LSIC) of the PZ-SIC to the local spin density approximation (LSDA). Here, we propose a new scaling factor to use in an LSIC-like approach that satisfies an additional important constraint: the correct coefficient of the atomic number Z in the asymptotic expansion of the exchange–correlation (xc) energy for atoms. LSIC and LSIC+ are scaled by functions of the iso-orbital indicator z σ , which distinguishes one-electron regions from many-electron regions. LSIC+ applied to the LSDA works better for many equilibrium properties than LSDA-LSIC and the Perdew, Burke, and Ernzerhof generalized gradient approximation (GGA), and almost close to the strongly constrained and appropriately normed (SCAN) meta-GGA. LSDA-LSIC and LSDA-LSIC+, however, fail to predict interaction energies involving weaker bonds, in sharp contrast to their earlier successes. It is found that more than one set of localized SIC orbitals can yield a nearly degenerate energetic description of the same multiple covalent bond, suggesting that a consistent chemical interpretation of the localized orbitals requires a new way to choose their Fermi orbital descriptors. To make a locally scaled down SIC to functionals beyond the LSDA requires a gauge transformation of the functional’s energy density. Here, the resulting SCAN-sdSIC, evaluated on SCAN-SIC total and localized orbital densities, leads to an acceptable description of many equilibrium properties including the dissociation energies of weak bonds.

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

NENCI-2021. I. A large benchmark database of non-equilibrium non-covalent interactions emphasizing close intermolecular contacts

In this work, we present NENCI-2021, a benchmark database of ~8000 Non-Equilibirum Non-Covalent Interaction energies for a large and diverse selection of intermolecular complexes of biological and chemical relevance. To meet the growing demand for large and high-quality quantum mechanical data in the chemical sciences, NENCI-2021 starts with the 101 molecular dimers in the widely used S66 and S101 databases and extends the scope of these works by (i) including 40 cation–π and anion–π complexes, a fundamentally important class of non-covalent interactions that are found throughout nature and pose a substantial challenge to theory, and (ii) systematically sampling all 141 intermolecular potential energy surfaces (PESs) by simultaneously varying the intermolecular distance and intermolecular angle in each dimer. Designed with an emphasis on close contacts, the complexes in NENCI-2021 were generated by sampling seven intermolecular distances along each PES (ranging from 0.7× to 1.1× the equilibrium separation) and nine intermolecular angles per distance (five for each ion–π complex), yielding an extensive database of 7763 benchmark intermolecular interaction energies (E int ) obtained at the coupled-cluster with singles, doubles, and perturbative triples/complete basis set [CCSD(T)/CBS] level of theory. The E int values in NENCI-2021 span a total of 225.3 kcal/mol, ranging from -38.5 to +186.8 kcal/mol, with a mean (median) E int value of -1.06 kcal/mol (-2.39 kcal/mol). In addition, a wide range of intermolecular atom-pair distances are also present in NENCI-2021, where close intermolecular contacts involving atoms that are located within the so-called van der Waals envelope are prevalent—these interactions, in particular, pose an enormous challenge for molecular modeling and are observed in many important chemical and biological systems. A detailed symmetry-adapted perturbation theory (SAPT)- based energy decomposition analysis also confirms the diverse and comprehensive nature of the intermolecular binding motifs present in NENCI-2021, which now includes a significant number of primarily induction-bound dimers (e.g., cation–π complexes). NENCI-2021 thus spans all regions of the SAPT ternary diagram, thereby warranting a new four-category classification scheme that includes complexes primarily bound by electrostatics (3499), induction (700), dispersion (1372), or mixtures thereof (2192). A critical error analysis performed on a representative set of intermolecular complexes in NENCI-2021 demonstrates that the E int values provided herein have an average error of ±0.1 kcal/mol, even for complexes with strongly repulsive E int values, and maximum errors of ±0.2–0.3 kcal/mol (i.e., ~±1.0 kJ/mol) for the most challenging cases. For these reasons, we expect that NENCI-2021 will play an important role in the testing, training, and development of next-generation classical and polarizable force fields, density functional theory approximations, wavefunction theory methods, and machine learning based intra- and inter-molecular potentials.

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

A deep potential model with long-range electrostatic interactions

Machine learning models for the potential energy of multi-atomic systems, such as the deep potential (DP) model, make molecular simulations with the accuracy of quantum mechanical density functional theory possible at a cost only moderately higher than that of empirical force fields. However, the majority of these models lack explicit long-range interactions and fail to describe properties that derive from the Coulombic tail of the forces. To overcome this limitation, we extend the DP model by approximating the long-range electrostatic interaction between ions (nuclei + core electrons) and valence electrons with that of distributions of spherical Gaussian charges located at ionic and electronic sites. The latter are rigorously defined in terms of the centers of the maximally localized Wannier distributions, whose dependence on the local atomic environment is modeled accurately by a deep neural network. In the DP long-range (DPLR) model, the electrostatic energy of the Gaussian charge system is added to short-range interactions that are represented as in the standard DP model. The resulting potential energy surface is smooth and possesses analytical forces and virial. Missing effects in the standard DP scheme are recovered, improving on accuracy and predictive power. By including long-range electrostatics, DPLR correctly extrapolates to large systems the potential energy surface learned from quantum mechanical calculations on smaller systems. We illustrate the approach with three examples: the potential energy profile of the water dimer, the free energy of interaction of a water molecule with a liquid water slab, and the phonon dispersion curves of the NaCl crystal.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Preliminary searches for spin-dependent interactions using sidebands of nuclear spin-precession signals

Various theories beyond the Standard Model predict new particles with masses in the sub-eV range with very weak couplings to ordinary matter. A new P-odd and T-odd interaction between polarized and unpolarized nucleons proportional to s⃗⋅r̂ is one such possibility, where r⃗=rr̂ is the spatial vector connecting the nucleons, and s⃗ is the spin of the polarized nucleon. Such an interaction involving a scalar coupling gsN at one vertex and a pseudoscalar coupling gpn at the polarized nucleon vertex can be induced by the exchange of spin-0 pseudoscalar bosons. We describe a new technique to search for interactions of this form and present the first measurements of this type. We show that future improvements to this technique can improve the laboratory upper bound on the product gsNgpn by two orders of magnitude for interaction ranges at the 100 micron scale.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Shock and contact interaction with a simple cubic array of particles

Shock-particle interaction is a fundamental pillar of multiphase compressible flows that has been studied at length for many decades. However, little attention has been paid to the interaction of particles with a contact interface that follows a shock in shock tube experiments and applications relating to blast waves. Presently, the phenomenon is studied at the microscale via particle resolved simulations of shock contact systems interacting with a structured array of particles as well as isolated particles. Simulations are conducted at particle volume fractions of 0%, 5%, 10%, 20%, and 40% at three contact Mach numbers. Additionally, the diaphragm position is varied, which controls the timing of the shock arrival time in relation to the contact arrival time. The modification to the drag on these stationary particles by the contact is analyzed and compared to the compressible Maxey–Riley–Gatignol model, which is adequate for the single particle cases but does not account for fluid mediated particle–particle interactions.

Mechanics↗
DOE OSTI2024

The rise and fall of stretched bond errors: Extending the analysis of Perdew–Zunger self-interaction corrections of reaction barrier heights beyond the LSDA

Incorporating self-interaction corrections (SIC) significantly improves chemical reaction barrier height predictions made using density functional theory methods. We present a detailed orbital-by-orbital analysis of these corrections for three semi-local density functional approximations (DFAs) situated on the three lowest rungs of Jacob’s ladder of approximations. The analysis is based on Fermi–Löwdin Orbital Self-Interaction Correction (FLOSIC) calculations performed at several steps along the reaction pathway from the reactants (R) to the transition state (TS) to the products (P) for four representative reactions selected from the BH76 benchmark set. For all three functionals, the major contribution to self-interaction corrections of the barrier heights can be traced to stretched bond orbitals that develop near the TS configuration. The magnitude of the ratio of the self-exchange–correlation energy to the self-Hartree energy (XC/H) for a given orbital is introduced as an indicator of one-electron self-interaction error. XC/H = 1.0 implies that an orbital’s self-exchange–correlation energy exactly cancels its self-Hartree energy and that the orbital, therefore, makes no contribution to the SIC in the FLOSIC scheme. For the practical DFAs studied here, XC/H spans a range of values. Here, the largest values are obtained for stretched or strongly lobed orbitals. We show that significant differences in XC/H for corresponding orbitals in the R, TS, and P configurations can be used to identify the major contributors to the SIC of barrier heights and reaction energies. Based on such comparisons, we suggest that barrier height predictions made using the strongly constrained and appropriately normed meta-generalized gradient approximation may have attained the best accuracy possible for a semi-local functional using the Perdew–Zunger SIC approach.

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

Multi frame radiography of supersonic water jets interacting with a foil target

Pulsed-power-driven underwater electrical explosion of cylindrical or conical wire arrays produces supersonic water jets that emerge from a bath, propagating through the air above it. Interaction of these jets with solid targets may represent a new platform for attaining materials at high pressure (>1010 Pa) conditions in a university-scale laboratory. However, measurements of the internal structure of such jets and how they interact with targets are difficult optically due to large densities and density contrasts involved. We utilized multi-frame x-ray radiographic imaging capabilities of the ID19 beamline at the European Synchrotron Radiation Facility to explore the water jet and its interaction with a 50 μm thick copper foil placed a few mm from the surface of water. The jet was generated with a ∼130 kA-amplitude current pulse of ∼450 ns rise time applied to a conical wire array. X-ray imaging revealed a droplet-type structure of the jet with an average density of <400 kg/m3 propagating with a velocity of ∼1400 m/s. Measurements of deformation and subsequent perforation of the target by the jet suggested pressures at the jet–target interface of ∼5 × 109 Pa. The results were compared to hydrodynamic simulations for better understanding of the jet parameters and their interaction with the foil target. These results can be used in future research to optimize the platform, and extend it to larger jet velocities in the case of higher driving currents supplied to the wire array.

Physics↗
DOE OSTI2024

Relativistic Douglas–Kroll–Hess calculations of hyperfine interactions within first-principles multireference methods

A relativistic magnetic hyperfine interaction Hamiltonian based on the Douglas–Kroll–Hess (DKH) theory up to the second order is implemented within the ab initio multireference methods, including spin–orbit coupling in the Molcas/OpenMolcas package. This implementation is applied to calculate relativistic hyperfine coupling (HFC) parameters for atomic systems and diatomic radicals with valence s or d orbitals by systematically varying active space size in the restricted active space self-consistent field formalism with restricted active space state interaction for spin–orbit coupling. The DKH relativistic treatment of the hyperfine interaction reduces the Fermi contact contribution to the HFC due to the presence of kinetic factors that regularize the singularity of the Dirac delta function in the nonrelativistic Fermi contact operator. This effect is more prominent for heavier nuclei. As the active space size increases, the relativistic correction of the Fermi contact contribution converges well to the experimental data for light and moderately heavy nuclei. The relativistic correction, however, does not significantly affect the spin-dipole contribution to the hyperfine interaction. In addition to the atomic and molecular systems, the implementation is applied to calculate the relativistic HFC parameters for large trivalent and divalent Tb-based single-molecule magnets (SMMs), such as Tb(III)Pc2 and Tb(II)(CpiPr5)2 without ligand truncation using well-converged basis sets. In particular, for the divalent SMM, which has an unpaired valence 6s/5d hybrid orbital, the relativistic treatment of HFC is crucial for a proper description of the Fermi contact contribution. Even with the relativistic hyperfine Hamiltonian, the divalent SMM is shown to exhibit strong tunability of HFC via an external electric field (i.e., strong hyperfine Stark effect).

Chemistry↗
DOE OSTI2025

Accurate noncovalent interactions in atomistic systems via quantum Drude oscillators

Accurately modeling polarization and van der Waals (vdW) interactions in atomistic systems typically requires high-level quantum-mechanical methods that are computationally expensive, hence limited in applicability. To address this challenge, efficient yet physically grounded models are needed—ones that not only enable accurate predictions but also provide insight into how noncovalent interactions scale in complex molecular and material systems. This review highlights the quantum Drude oscillator (QDO) model, a physically motivated and computationally efficient framework that captures the essential features of electronic response, including polarization and dispersion forces, across a wide range of chemical and material systems. We discuss how the QDO model quantitatively reproduces the polarization response of many-electron atoms and how key components of noncovalent interactions—exchange-repulsion, polarization, and dispersion—emerge naturally in QDO dimers. Furthermore, the model provides predictive scaling laws that elucidate trends in polarizability and dispersion across the periodic table and in molecular assemblies. By uniting interpretability, accuracy, and efficiency, the QDO model offers a versatile approach for modeling noncovalent interactions in systems ranging from isolated molecules to complex condensed phases and nanostructured materials.

Khabibrakhmanov, Almaz [Univ. of Luxembourg, Luxem↗
DOE OSTI2021

Ion-dependent protein–surface interactions from intrinsic solvent response

Significance Hard–soft interfaces between inorganic surfaces and biomolecules promote self-assembly processes with broad implications in biogeochemistry, energy sciences, nanomedicine, and origins of life. Yet, detailed molecular-scale understanding of inorganic–biomolecule interactions and their dependence on solution conditions is missing. We present a theory for the initial stages of inorganic–biomolecule assembly based on the far-field response of water, using experimentally characterized interactions between muscovite surfaces and mica-binding proteins as model systems. Our work connects molecular details of the solution to assembly outcomes and suggests the initial driving forces for assembly are dominated by long-range, ion-specific interactions. The connections made between interfacial structure and long-range surface–biomolecule interactions provide insights toward a predictive understanding of biomolecular self-assembly on mineral surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗