Machine learning the electric field response of condensed phase systems using perturbed neural network potentials.

The interaction of condensed phase systems with external electric fields is of major importance in a myriad of processes in nature and technology, ranging from the field-directed motion of cells (galvanotaxis), to geochemistry and the formation of ice phases on planets, to field-directed chemical catalysis and energy storage and conversion systems including supercapacitors, batteries and solar cells. Molecular simulation in the presence of electric fields would give important atomistic insight into these processes but applications of the most accurate methods such as ab-initio molecular dynamics (AIMD) are limited in scope by their computational expense. Here we introduce Perturbed Neural Network Potential Molecular Dynamics (PNNP MD) to push back the accessible time and length scales of such simulations. We demonstrate that important dielectric properties of liquid water including the field-induced relaxation dynamics, the dielectric constant and the field-dependent IR spectrum can be machine learned up to surprisingly high field strengths of about 0.2 V Å-1 without loss in accuracy when compared to ab-initio molecular dynamics. This is remarkable because, in contrast to most previous approaches, the two neural networks on which PNNP MD is based are exclusively trained on molecular configurations sampled from zero-field MD simulations, demonstrating that the networks not only interpolate but also reliably extrapolate the field response. PNNP MD is based on rigorous theory yet it is simple, general, modular, and systematically improvable allowing us to obtain atomistic insight into the interaction of a wide range of condensed phase systems with external electric fields.

Resolving intermediates during the growth of aluminum deuteroxide (Hydroxide) polymorphs in high chemical potential solutions.

Aluminum hydroxide polymorphs are of widespread importance yet their kinetics of nucleation and growth remain beyond the reach of current models. Here we attempt to unveil the reaction processes underlying the polymorphs formation at high chemical potential. We examine their formation in-situ from supersaturated alkaline sodium aluminate solutions using deuteration and time-resolved neutron pair distribution function analyses, which indicate the formation of individual Al(OD)3 layers as an intermediate particle phase. These layers ultimately stack to form gibbsite- or bayerite-like layered heterostructures. Ex-situ characterization of the recovered precipitates using 27Al magic angle spinning nuclear magnetic resonance spectroscopy, Raman, X-ray diffraction, and scanning electron microscopy, suggests the presence of additional intermediate states, an amorphous compound bearing both tetrahededrally- and penta-coordinated Al3+. These observations reveal the complex pathways to form Al(OD)3 monolayers via either transient pentacoordinate species or amorphous-to-ordered transitions. The subsequent crystallization of admixed gibbsite/bayerite is followed by an Al(OD)3 monolayer attachment process.

Uncovering the Size-Dependent Thermal Solid Transformation of Akaganéite.

Investigating the structural evolution and phase transformation of iron oxides is crucial for gaining a deeper understanding of geological changes on diverse planets and preparing oxide materials suitable for industrial applications. In this study, in-situ heating techniques are employed in conjunction with transmission electron microscopy (TEM) observations and ex-situ characterization to thoroughly analyze the thermal solid-phase transformation of akaganéite 1D nanostructures with varying diameters. These findings offer compelling evidence for a size-dependent morphology evolution in akaganéite 1D nanostructures, which can be attributed to the transformation from akaganéite to maghemite (γ-Fe2O3) and subsequent crystal growth. Specifically, it is observed that akaganéite nanorods with a diameter of ∼50 nm transformed into hollow polycrystalline maghemite nanorods, which demonstrated remarkable stability without arresting crystal growth under continuous heating. In contrast, smaller akaganéite nanoneedles or nanowires with a diameter ranging from 20 to 8 nm displayed a propensity for forming single-crystal nanoneedles or nanowires through phase transformation and densification. By manipulating the size of the precursors, a straightforward method is developed for the synthesis of single-crystal and polycrystalline maghemite nanowires through solid-phase transformation. These significant findings provide new insights into the size-dependent structural evolution and phase transformation of iron oxides at the nanoscale.

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics.

The dynamics, orientational anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO2), and lithium nitrate (LiNO3), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. The 2D IR, NMR, and viscosity results show that LiNO2 exhibits longer correlation times, lower diffusivity, and nearly 4 times greater viscosity compared to those of the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water-ion network interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO2 and LiNO3 solutions show significantly weakened chemical interactions between the lithium cations and the methyl thiocyanate when compared with those of the lithium halide salts.

Effect of impurities on radical formation in gibbsite radiolysis.

The generation and stabilization of gamma radiation-induced hydrogen atoms in gibbsite (Al(OH)3) nanoplates is directly related to the nature of residual ions from synthetic precursors used, whether nitrates or chlorides. The concentration of hydrogen atoms trapped in the interstitial layers of gibbsite is lower and decays faster in comparison to boehmite (AlOOH), which could affect the management of these materials in radioactive waste.

Development and application of hybrid AIMD/cDFT simulations for atomic-to-mesoscale chemistry.

Many important chemical processes involve reactivity and dynamics in complex solutions. Gaining a fundamental understanding of these reaction mechanisms is a challenging goal that requires advanced computational and experimental approaches. However, important techniques such as molecular simulation have limitations in terms of scales of time, length, and system complexity. Furthermore, among the currently available solvation models, there are very few designed to describe the interaction between the molecular scale and the mesoscale. To help address this challenge, here, we establish a novel hybrid approach that couples first-principles plane-wave density functional theory with classical density functional theory (cDFT). In this approach, a region of interest described by ab initio molecular dynamics (AIMD) interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. cDFT is a robust but efficient mesoscopic approach to accurate thermodynamics of bulk electrolyte solutions over a wide concentration range (up to 2M concentrations). Benchmarking against commonly used continuum models of solvation, such as SMD, as well as experiments, demonstrates that our hybrid AIMD-cDFT method is able to produce reasonable solvation energies for a variety of molecules and ions. With this model, we also examined the solvent effects on a prototype SN2 reaction of the nucleophilic attack of a chloride ion on methyl chloride in the solution. The resulting reaction pathway profile and the solution phase barrier agree well with experiment, showing that our AIMD/cDFT hybrid approach can provide insight into the specific role of the solvent on the reaction coordinate.

Facet-dependent dispersion and aggregation of aqueous hematite nanoparticles.

Nanoparticle aggregates in solution controls surface reactivity and function. Complete dispersion often requires additive sorbents to impart a net repulsive interaction between particles. Facet engineering of nanocrystals offers an alternative approach to produce monodisperse suspensions simply based on facet-specific interaction with solvent molecules. Here, we measure the dispersion/aggregation of three morphologies of hematite (α-Fe2O3) nanoparticles in varied aqueous solutions using ex situ electron microscopy and in situ small-angle x-ray scattering. We demonstrate a unique tendency of (104) hematite nanoparticles to maintain a monodisperse state across a wide range of solution conditions not observed with (001)- and (116)-dominated particles. Density functional theory calculations reveal an inert, densely hydrogen-bonded first water layer on the (104) facet that favors interparticle dispersion. Results validate the notion that nanoparticle dispersions can be controlled through morphology for specific solvents, which may help in the development of various nanoparticle applications that rely on their interfacial area to be highly accessible in stable suspensions.

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.

First principles simulations of MgO(100) surface hydration at ambient conditions.

Developing a better understanding of water ordering and hydroxylation at oxide mineral surfaces is important across a breath of application spaces. Recent vibrational sum frequency generation (vSFG) measurements on MgO(100) surfaces at ambient conditions showed that water dissociates and hydroxylates the surface yielding a non-hydrogen bonded hydroxyl species. Starting from previously determined water hydroxylation patterns on MgO(100), we performed ab initio thermodynamic calculations and vibrational analysis to compare with the vSFG observations. At ambient conditions (i.e., T = 298.15 K and pH2O = 32 mbar), the most thermodynamically favorable surface hydroxylation is found to be p(3 × 2) - 8H2O, involving a dissociation of 25% of the adsorbed water. Analysis of the vibrational density of states for this hydroxylation configuration yielded three different hydrogen bonding environments with the frequency of the peaks in very good agreement with the vSFG measurements. However, the non-H-bonded spectral feature on this surface is predicted to be similar to that expected for Mg(OH)2, a thermodynamically downhill alteration of the surface that must be independently ruled out before one can be fully confident in the apparent theory/vSFG agreement. Our study provides more insights into the ordering and structure of water monolayer at MgO(100) surface at ambient conditions and completes previous theoretical and experimental analysis performed at low temperature and ultra-high vacuum conditions.

Electronic Structure of Actinyls: Orbital Properties.

A detailed analysis is presented for the covalent character of the orbitals in the actinyls: UO22+, NpO22+, and PuO22+. Both the initial, or ground state, GS, configuration and the excited configurations where a 3d electron is excited into the open valence, nominally the 5f shell, are considered. The orbitals are determined as fully relativistic, four component Dirac-Coulomb Hartree-Fock solutions. Several measures, which go beyond the commonly used population analyses, are used to characterize the covalent character of an orbital in order to obtain reliable estimates of the covalency. Although there are differences in the covalent character of the orbitals for the initial and excited configurations of the different actinyls, there is a surprising similarity in the covalent character for all of the states considered. This is true both between the initial and excited configurations as well as between the different actinyls. The analysis emphasizes the 5f covalent character in the closed shell bonding orbitals and the open shell antibonding orbitals since the focus is on characterizing orbitals needed in a many-body treatment of the actinyl wave functions. However, estimates are also made of the participation of the actinide 6d in the covalent bonding.

Effect of Adsorbed Carboxylates on the Dissolution of Boehmite Nanoplates in Highly Alkaline Solutions.

Understanding the dissolution of boehmite in highly alkaline solutions is important to processing complex nuclear waste stored at the Hanford (WA) and Savannah River (SC) sites in the United States. Here, we report the adsorption of model carboxylates on boehmite nanoplates in alkaline solutions and their effects on boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate occurred at pH 13, with adsorption decreasing linearly to 3 M NaOH. Classical molecular dynamics simulations suggest that the adsorption of oxalate dianions onto the boehmite surface under high pH can occur through either inner- or outer-sphere complexation mechanisms depending on adsorption sites. However, both adsorption models indicate relatively weak binding, with an energy preference of 1.26 to 2.10 kcal/mol. By preloading boehmite nanoplates with oxalate or acetate, we observed suppression of dissolution rates by 23 or 10%, respectively, compared to pure solids. Scanning electron microscopy and transmission electron microscopy characterizations revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. We conclude that preadsorbed carboxylates can persist on boehmite surfaces, decreasing the density of dissolution-active sites and thereby adding extrinsic controls on dissolution rates.

Tracking nitrite's deviation from Stokes-Einstein predictions with pulsed field gradient 15N NMR spectroscopy.

Predicting the behavior of oxyanions in radioactive waste stored at the Department of Energy legacy nuclear sites requires the development of novel analytical methods. This work demonstrates 15N pulsed field gradient nuclear magnetic resonance spectroscopy to quantify the diffusivity of nitrite. Experimental results, supported by molecular dynamics simulations, indicate that the diffusivity of free hydrated nitrite exceeds that of free hydrated sodium despite the greater hydrodynamic radius of nitrite. Investigations are underway to understand how the compositional and dynamical heterogeneities of the ion networks at high concentrations affect rheological and transport properties.

Tracking Initial Fe(II)-Driven Ferrihydrite Transformations: A Mössbauer Spectroscopy and Isotope Investigation.

Transformation of nanocrystalline ferrihydrite to more stable microcrystalline Fe(III) oxides is rapidly accelerated under reducing conditions with aqueous Fe(II) present. While the major steps of Fe(II)-catalyzed ferrihydrite transformation are known, processes in the initial phase that lead to nucleation and the growth of product minerals remain unclear. To track ferrihydrite-Fe(II) interactions during this initial phase, we used Fe isotopes, Mössbauer spectroscopy, and extractions to monitor the structural, magnetic, and isotope composition changes of ferrihydrite within ∼30 min of Fe(II) exposure. We observed rapid isotope mixing between aqueous Fe(II) and ferrihydrite during this initial lag phase. Our findings from Mössbauer spectroscopy indicate that a more magnetically ordered Fe(III) phase initially forms that is distinct from ferrihydrite and bulk crystalline transformation products. The signature of this phase is consistent with the early stage emergence of lepidocrocite-like lamellae observed in previous transmission electron microscopy studies. Its signature is furthermore removed by xylenol extraction of Fe(III), the same approach used to identify a chemically labile form of Fe(III) resulting from Fe(II) contact that is correlated to the ultimate emergence of crystalline product phases detectable by X-ray diffraction. Our work indicates that the mineralogical changes in the initial lag phase of Fh transformation initiated by Fe(II)-Fh electron transfer are critical to understanding ferrihydrite behavior in soils and sediments, particularly with regard to metal uptake and release.

Crystal dissolution by particle detachment.

Crystal dissolution, which is a fundamental process in both natural and technological settings, has been predominately viewed as a process of ion-by-ion detachment into a surrounding solvent. Here we report a mechanism of dissolution by particle detachment (DPD) that dominates in mesocrystals formed via crystallization by particle attachment (CPA). Using liquid phase electron microscopy to directly observe dissolution of hematite crystals - both compact rhombohedra and mesocrystals of coaligned nanoparticles - we find that the mesocrystals evolve into branched structures, which disintegrate as individual sub-particles detach. The resulting dissolution rates far exceed those for equivalent masses of compact single crystals. Applying a numerical generalization of the Gibbs-Thomson effect, we show that the physical drivers of DPD are curvature and strain inherently tied to the original CPA process. Based on the generality of the model, we anticipate that DPD is widespread for both natural minerals and synthetic crystals formed via CPA.

Predicting Outcomes of Nanoparticle Attachment by Connecting Atomistic, Interfacial, Particle, and Aggregate Scales.

Predicting nanoparticle aggregation and attachment phenomena requires a rigorous understanding of the interplay among crystal structure, particle morphology, surface chemistry, solution conditions, and interparticle forces, yet no comprehensive picture exists. We used an integrated suite of experimental, theoretical, and simulation methods to resolve the effect of solution pH on the aggregation of boehmite nanoplatelets, a case study with important implications for the environmental management of legacy nuclear waste. Real-time observations showed that the particles attach preferentially along the (010) planes at pH 8.5 and the (101) planes at pH 11. To rationalize these results, we established the connection between key physicochemical phenomena across the relevant length scales. Starting from molecular-scale simulations of surface hydroxyl reactivity, we developed an interfacial-scale model of the corresponding electrostatic potentials, with subsequent particle-scale calculations of the resulting driving forces allowing successful prediction of the attachment modes. Finally, we scaled these phenomena to understand the collective structure at the aggregate-scale. Our results indicate that facet-specific differences in surface chemistry produce heterogeneous surface charge distributions that are coupled to particle anisotropy and shape-dependent hydrodynamic forces, to play a key role in controlling aggregation behavior.

An Efficient Reactive Force Field without Explicit Coordination Dependence for Studying Caustic Aluminum Chemistry.

Reactive force fields (RFFs) are an expedient approach to sample chemical reaction paths in complex systems, relative to density functional theory. However, there is continued need to improve efficiencies, specifically in systems that have slow transverse degrees of freedom, as in highly viscous and superconcentrated solutions. Here, we present an RFF that is differentiated from current models (e.g., ReaxFF) by omitting explicit dependence on the atom coordination and employing a small parameter set based on Lennard-Jones, Gaussian, and Stillinger-Weber potentials. The model was parametrized from AIMD simulation data and is used to model aluminate reactivity in sodium hydroxide solutions with extensive validation against experimental radial distribution functions, computed free energy profiles for oligomerization, and formation energies. The model enables simulation of early stage Al(OH)3 nucleation which has significant relevance to industrial processing of aluminum and has a computational cost that is reduced by 1 order of magnitude relative to ReaxFF.

Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions.

Ultraviolet (UV) photolysis of nitrite ions (NO2-) in aqueous solutions produces a suite of radicals, viz., NO·, O-, ·OH, and ·NO2. The O- and NO· radicals are initially formed from the dissociation of photoexcited NO2-. The O- radical undergoes reversible proton transfer with water to generate ·OH. Both ·OH and O- oxidize the NO2- to ·NO2 radicals. The reactions of ·OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO·, ·OH, and ·NO2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO2- solvation were determined to alter the initial yields of ·NO and ·OH radicals as well as alter the reactivity of NO2- toward ·OH, impacting the production of ·NO2. The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

Understanding the mechanisms of anisotropic dissolution in metal oxides by applying radiolysis simulations to liquid-phase TEM.

Iron-based redox-active minerals are ubiquitous in soils, sediments, and aquatic systems. Their dissolution is of great importance for microbial impacts on carbon cycling and the biogeochemistry of the lithosphere and hydrosphere. Despite its widespread significance and extensive prior study, the atomic-to-nanoscale mechanisms of dissolution remain poorly understood, particularly the interplay between acidic and reductive processes. Here, we use in situ liquid-phase-transmission electron microscopy (LP-TEM) and simulations of radiolysis to probe and control acidic versus reductive dissolution of akaganeite (ß-FeOOH) nanorods. Informed by crystal structure and surface chemistry, the balance between acidic dissolution at rod tips and reductive dissolution at rod sides was systematically varied using pH buffers, background chloride anions, and electron beam dose. We find that buffers, such as bis-tris, effectively inhibited dissolution by consuming radiolytic acidic and reducing species such as superoxides and aqueous electrons. In contrast, chloride anions simultaneously suppressed dissolution at rod tips by stabilizing structural elements while promoting dissolution at rod sides through surface complexation. Dissolution behaviors were systematically varied by shifting the balance between acidic and reductive attacks. The findings show LP-TEM combined with simulations of radiolysis effects can provide a unique and versatile platform for quantitatively investigating dissolution mechanisms, with implications for understanding metal cycling in natural environments and the development of tailored nanomaterials.

Oxide- and Silicate-Water Interfaces and Their Roles in Technology and the Environment.

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.