First-principles Simulations Research Articles

Rational construction of ZnIn2S4/Co3Se4 with boosted photocatalytic hydrogen production through cooperate with S-scheme heterojunction and photothermal effect

The rational design of excellent visible light photocatalysts that efficiently utilize the solar spectrum is urgently needed. In this work, ZnIn2S4 (ZIS) and Co3Se4 (CS) were coupled by a multistep process involving simple ultrasonic self-assembly and calcination to form ZnIn2S4/Co3Se4 (ZIS/CS) photocatalysts with synergistic S-scheme heterojunctions and photothermal effects, which realized efficient photocatalytic hydrogen (H2) production with optimal H2 yield of 2.46 mmol h−1 g−1, superior to pure ZIS (0.47 mmol h−1 g−1) by a factor of 5.23. The excellent cyclic stability and wide environmental adaptability to the ionic environment of water of ZIS/CS were proved. The positive impaction of photothermal effect on the H2 yield of ZIS/CS was investigated and confirmed by the temperature change of photocatalysts powder or photocatalytic system under light irradiation. In addition, based on a series of characterization analyses and first-principle simulation calculations, a charge transfer pathway for ZIS/CS S-scheme heterojunctions was proposed. This work provides valuable ideas and feasible research methods for the design of stable and practical photocatalysts.

Ab Initio Kinetic Pathway of Diborane Decomposition on Transition Metal Surfaces in Borophene Chemical Vapor Deposition Growth.

The chemical vapor deposition (CVD) method holds promise for the scalable and controlled synthesis of high-quality borophene. However, the current lack of an atomistic understanding of intricate kinetic pathways from precursors to borophene impedes process optimization. Here, we employ first-principles simulations to systematically explore the pyrolytic decomposition pathways of the most used precursor diborane (B2H6) to borophene on various transition metal surfaces. Our results reveal that B2H6 on various metal substrates exhibits different dissociation behaviors. Meanwhile, the activity of the examined metal substrates is quite anisotropic and surface direction-dependent, where the estimated overall catalytic activity order of these metals is found to be Pd ≈ Pt ≈ Rh > Ir ≈ Ru ≈ Cu > Au ≈ Ag. Our study provides atomistic insights into the dissociation kinetics of diborane precursors on various transition metal surfaces, serving as a guide for experimental growth of borophene.

Unveiling Versatile Electronic Properties and Contact Features of Metal-Semiconductor Graphene/γ-Ge2SSe van der Waals Heterostructures.

Recently, searching for a metal-semiconductor junction (MSJ) that exhibits low-contact resistance has received tremendous consideration, as they are essential components in next-generation field-effect transistors. In this work, we design a MSJ by integrating two-dimensional (2D) graphene as the metallic electrode and 2D Janus γ-Ge2SSe as the semiconducting channel using first-principles simulations. All the graphene/γ-Ge2SSe MSJs are predicted to be energetically, mechanically, and thermodynamically stable, characterized by the weak van der Waals (vdW) interactions. The graphene/γ-SGe2Se MSJ-vdWH form the n-type Schottky contact (SC), while the graphene/γ-SeGe2S MSJ-vdWH form the p-type one, suggesting that the switching between p-type and n-type SC in the graphene/γ-Ge2SSe MSJ-vdWHs can occur spontaneously by simply altering the stacking patterns, without requiring any external conditions. Notably, the contact features, including contact types and barriers of the graphene/γ-Ge2SSe MSJs are significant in versatility and can be altered by applying electric gating and adjusting interlayer spacing. Both the applied electric gating and strain engineering induce switchability between p- and n-type and SC to OC in the graphene/γ-Ge2SSE MSJs. This versatility underscores the potential of the graphene/γ-Ge2SSe MSJ for next-generation applications that require low-contact resistance and high performance.

Rigidly Axial O Coordination-Induced Spin Polarization on Single Ni-N4-C Site by MXene Coupling for Boosting Electrochemical CO2 Reduction to CO.

Regulating the spin states in transition-metal (TM)-based single-atom catalysts (SACs), such as the TM-Nx-C configurations, is crucial for improving the catalytic activity. However, the role of spin in single Ni atoms facilitating the electrochemical CO2 reduction reaction (CO2RR) has been largely overlooked. Using first-principles simulations, we investigated the electrocatalytic performance of Ni-N4-C SACs vertically stacked on the O-terminated MXene nanosheets for the CO2RR. The terminated O atoms on MXene axially interact with the Ni atom due to significant charge transfer between them. Unlike the pure Ni-N4 site, which lacks spin polarization, the newly formed Ni-N4O configuration breaks the spin degeneracy of Ni d orbitals, dramatically lifting the energy level of spin-down d orbitals relative to that of spin-up d orbitals. As a result, the d electrons of Ni in the two spin channels are rearranged, leading to large net spin moments of 1.4 μB. Compared to the Ni-N4 site, the partially filled minority-spin dz2 orbitals of Ni on Ni-N4O weaken the occupied d-π* orbitals between Ni and *COOH, significantly stabilizing the key intermediate. The detailed reaction mechanisms and energetics show that four MXenes, namely, Hf3C2, Zr3C2, Hf2C, and Zr2C, can induce a large spin on the Ni site, thereby improving catalytic activity for CO2 reduction to CO, with a lower onset potential of about -0.75 V vs SHE compared to pure Ni SACs (-1.17 V) according to the potential-constant model with an explicit solvent environment.

Heterogeneity in Point Defect Distribution and Mobility in Solid Ion Conductors.

Alkali metal anodes paired with solid ion conductors offer promising avenues for enhancing battery energy density and safety. To facilitate rapid ion transport crucial for fast charging and discharging of batteries, it is essential to understand the behavior of point defects in these conductors. In this study, we investigate the heterogeneity of defect distribution in two prototypical solid ion conductors, Li3OCl and Li2PO2N (LiPON), by quantifying the defect formation energy (DFE) as a function of distance from the surface and interface through first-principles simulations. To simulate defects at the electrode-electrolyte interface, we perform calculations of Li+ vacancy in Li3OCl near its interface with lithium metal. Our results reveal a significant difference between the bulk and surface/interface DFE which could lead to defect aggregation/depletion near the surface/interface. Interestingly, while Li3OCl has a lower surface DFE than the bulk in most cases, LiPON follows the opposite trend with a higher surface DFE compared to the bulk. Due to this difference between bulk and surface DFE, the defect density can be up to 14 orders of magnitude higher at surfaces compared to the bulk. Further, we reveal that the DFE transition from surface/interface to bulk is precisely characterized by an exponentially decaying function. By incorporating this exponential trend, we develop a revised model for the average behavior of defects in solid ion conductors that offers a more accurate description of the influence of grain sizes. Surface effects dominate for grain sizes ≲1 μm, highlighting the importance of surface defect engineering and the DFE function for accurately capturing ion transport in devices. We further explore the kinetics of defect redistribution by calculating the migration barriers for defect movement between bulk and surfaces. We find a highly asymmetric energy landscape for the lithium vacancies, exhibiting lower migration barriers for movement toward the surface compared to the bulk, while interstitial defects exhibit comparable kinetics between surface and bulk regions. These insights highlight the importance of considering both thermodynamic and kinetic factors in designing solid ion conductors for improved ion transport at surfaces and interfaces.

Investigation of phase transformation model, densification mechanism, and mechanical properties of TiH2 powder metallurgy materials

TiH2 has gradually gained attention in powder metallurgy because of its unique properties. This study systematically investigated the porosity, density, mechanical tensile properties, and fracture toughness of sintered samples of TiH2 as a powder metallurgy starting material. The results showed that, compared with hydrogenation-dehydrogenation titanium (HDH Ti), the density, elongation, and fracture toughness of the sintered TiH2 samples significantly improved. In addition, the contributions of grain size, porosity, and oxygen content to the yield strength of the samples are discussed, and the results revealed that a lower oxygen content and porosity are the main reasons for the differences in the mechanical properties between HDH Ti and TiH2. Finally, the experimental results are combined with first-principles calculations and simulations to construct a TiH2 phase transition model. The contribution of H atoms to the TiH2 phase transition energy barrier and activation sintering densification was investigated and elucidated, revealing the TiH2 sintering densification mechanism from the perspective of phase transition. The derived results contribute to a deeper understanding of the intrinsic mechanism of TiH2 activation sintering densification, which is highly important for the development of advanced titanium materials.

Giant Photocaloric Effects across a Vast Temperature Range in Ferroelectric Perovskites.

Solid-state cooling presents an energy-efficient and environmentally friendly alternative to traditional refrigeration technologies that rely on thermodynamic cycles involving greenhouse gases. However, conventional caloric effects face several challenges that impede their practical application in refrigeration devices. First, operational temperature conditions must align closely with zero-field phase-transition points; otherwise, the required driving fields become excessively large. However, phase transitions occur infrequently near room temperature. Additionally, caloric effects typically exhibit strong temperature dependence and are sizable only within relatively narrow temperature ranges. In this Letter, we employ first-principles simulation methods to demonstrate that light-driven phase transitions in polar oxide perovskites have the potential to overcome such limitations. Specifically, for the prototypical ferroelectric KNbO_{3} we illustrate the existence of giant "photocaloric" effects induced by light absorption (ΔS_{PC}∼100 J K^{-1} kg^{-1} and ΔT_{PC}∼10 K) across a vast temperature range of several hundred Kelvin, encompassing room temperature. These findings are expected to be generalizable to other materials exhibiting similar polar behavior.

Unraveling the catalytic performance of RuO2(1 1 0) for highly-selective ethylene production from methane at low temperature: Insights from first-principles and microkinetic simulations

Despite significant progress in low-temperature methane (CH4) activation, commercial viability, specifically obtaining high yields of C1/C2 products, remains a challenge. High desorption energy (>2 eV) and overoxidation of the target products are key limitations in CH4 utilization. Herein, we employ first-principles density functional theory (DFT) and microkinetics simulations to investigate the CH4 activation and the feasibility of its conversion to ethylene (C2H4) on the RuO2 (1 1 0) surface. The CH activation and CH4 dehydrogenation processes are thoroughly investigated, with a particular focus on the diffusion of surface intermediates. The results show that the RuO2 (1 1 0) surface exhibits high reactivity in CH4 activation (Ea = 0.60 eV), with CH3 and CH2 are the predominant species, and CH2 being the most mobile intermediate on the surface. Consequently, self-coupling of CH2* species via CC coupling occurs more readily, yielding C2H4, a potential raw material for the chemical industry. More importantly, we demonstrate that the produced C2H4 can easily desorb under mild conditions due to its low desorption energy of 0.97 eV. Microkinetic simulations based on the DFT energetics indicate that CH4 activation can occur at temperatures below 200 K, and C2H4 can be desorbed at room temperature. Further, the selectivity analysis predicts that C2H4 is the major product at low temperatures (300–450 K) with 100 % selectivity, then competes with formaldehyde at intermediate temperatures in the CH4 conversion over RuO2 (1 1 0) surface. The present findings suggest that the RuO2 (1 1 0) surface is a potential catalyst for facilitating ethylene production under mild conditions.

Unraveling the electronic properties in SiO2 under ultrafast laser irradiation

First-principles simulations were conducted to explore various electronic properties of crystalline SiO2 (α-quartz) under ultrafast laser irradiation. Employing Density Functional Perturbation Theory and the many-body (GW) approximation, we calculated the impact of thermally excited electrons on the electronic specific heat, electron pressure, effective mass, deformation potential, electron-phonon coupling and electron relaxation time of quartz, covering a wide range of electron temperatures, up to 100,000 K. We show that the electron-phonon relaxation time of highly-excited quartz becomes twice faster compared to low-excited states. The deformation potential, which dictates atomic displacement, has a non-monotonic behavior with a well-pronounced minimum at around 16,000 K (2.7 × 1021 cm−3 of excited electrons) where the bond ionicity of the Si-O starts decreasing followed by a cohesion loss at 35,000 K due to the pressure exerted by the excited electrons on the lattice. Consequently, our calculated data, illustrating the evolution of physical parameters, can facilitate simulations of laser-matter interactions and provide predictive insights into the behavior of quartz under experimental conditions.

Physics-inspired AI-based model for cold crushing strength of an iron ore pellet plant

ABSTRACT The cold crushing strength (CCS) of iron ore pellets produced in a straight grate indurating machine is critical to their quality and performance. This study explored two modelling approaches to accurately predict CCS: an artificial neural network (ANN) model and a physics-informed hybrid model. The ANN model was designed to predict CCS directly from parameters such as pellet chemistry, Blaine number, and measured induration conditions. In contrast, the hybrid model combined a first-principles simulation of the induration process with the ANN model, using the simulated pellet temperatures and the exit gas temperatures as inputs to the ANN component, while keeping the other input parameters the same as the standalone ANN model. The models were validated using 1730 datasets from a 6 MTPA iron ore pelletizing plant of Tata Steel India Ltd. The hybrid model demonstrated superior performance, achieving a mean absolute percentage error (MAPE) of 3.7% compared to 4.1% for the ANN-only model. The hybrid model offers two key advantages: (1) it can provide early insights into CCS, enabling pre-emptive adjustments to the induration process, and (2) it can be used as a powerful optimization tool to enhance the overall quality and consistency of the iron ore pellets.

Engineering active and robust alloy-based electrocatalyst by rapid Joule-heating toward ampere-level hydrogen evolution

Rational design of bimetallic alloy is an effective way to improve the electrocatalytic activity and stability of Mo-based cathode for ampere-level hydrogen evolution. However, it is still critical to realise desirable syntheses due to the wide reduction potentials between different metal elements and uncontrollable nucleation processes. Herein, we propose a rapid Joule heating method to effectively load RuMo alloy onto MoOx matrix. As-prepared catalyst exhibits excellent stability (2000 h @ 1000 mA cm−2) and ultralow overpotential (9 mV, 18 mV and 15 mV in 1 M KOH, 1 M PBS, 0.5 M H2SO4 solution, respectively) at 10 mA cm−2. Based on first-principle simulations and operando measurements, the impressive electrocatalytic stability and activity are investigated. And the role of rapid Joule heating method is highlighted and discussed in details. This study showcases rapid Joule heating as a feasible strategy to construct highly efficient alloy-based electrocatalysts.

Spontaneous ignition and flame propagation in hydrogen/methane wrinkled laminar flames at reheat conditions: Effect of pressure and hydrogen fraction

Direct numerical simulations (DNS) with detailed chemical kinetics and chemical explosive mode analysis (CEMA) are performed to investigate the effect of operating pressure and hydrogen–methane blending on laminar wrinkled flames at reheat combustion conditions. Building upon previous three-dimensional DNS datasets of reheat hydrogen flames, the present work considers two-dimensional configurations that render computationally-feasible simulations of high-pressure combustion and significantly more complex hydrocarbon chemistry. A geometrically-simplified representation of the reheat combustor is adopted and the thermodynamic states considered in the simulations are carefully chosen to mimic gas turbine operation conditions, which are constrained to achieve a target flame position and flame temperature. The two-dimensional DNS results are first assessed against the available three-dimensional data and then analyzed to extract the main trends exhibited by the reheat combustion process with respect to the fraction of the fuel consumed by spontaneous ignition and flame propagation, for increasing pressures and hydrogen fractions. Due to significant differences in the characteristic features of the velocity and thermal boundary layers between the three-dimensional and the two-dimensional configurations, a different global flame shape is observed (V-shaped flame vs W-shape flame) together with a ∼10% bias in the fraction of fuel consumed by spontaneous ignition. Crucially, results from the scaling studies reveal very clear trends with a significant decrease in the fuel consumption by spontaneous ignition for increasing pressures and hydrogen fractions, at the conditions investigated. Finally, this study highlights the important role that first-principle direct numerical simulations, even when conducted in computationally affordable two-dimensional simplified geometrical configurations, can play in obtaining detailed insights and quantitative trends useful for the characterization of complex reactive flows.Novelty and significanceThe reheat burners of the two-stage sequential gas turbine combustors are designed to stabilize flames primarily due to spontaneous ignition. However, prior numerical simulations revealed the presence of an additional assisted-ignition mode aided by recirculation zones. In this study, we used practically feasible two-dimensional direct numerical simulations of premixed hydrogen–air mixtures under lean conditions to quantify the roles of the two flame stabilization modes at different operating pressures. Achieving fundamental understanding of the effect of pressure and hydrogen fraction on flame stabilization is crucial to the development of two-stage sequential combustion and the present two-dimensional calculations provide important new insights. We show that at high pressures, both modes consume fuel to a similar extent. We also investigated the effect of methane blending on flame stabilization. This study also discusses how two-dimensional direct numerical simulations can be leveraged in the design optimization of reheat burners at low technology readiness levels.

Generating 4-dimensional wormholes with Yang–Mills Casimir sources

This work presents a new static and spherically symmetric traversable wormhole solution in General Relativity, which is supported by the quantum vacuum fluctuations associated with the Casimir effect of the Yang–Mills field confined between perfect chromometallic mirrors in (3+1) dimensions, recently fitted using first-principle numerical simulations. Initially, we employ a perturbative approach for x=mr≪1, where m represents the Casimir mass and r is the radial coordinate. This approach has proven to be a reasonable approximation when compared with the exact case in this regime. To find well-behaved redshift functions, we impose constraints on the free parameters. As expected, this solution recovers the electromagnetic-like Casimir solution for m=0. Analyzing the traversability conditions, we graphically find that all are satisfied for 0≤m≤0.17. On the other hand, all the energy conditions are violated, as usual in this context due to the quantum origin of the source. Stability from Tolman–Oppenheimer–Volkov (TOV) equation is guaranteed for all r and from the speed of sound for 0.16≤m≤0.18. Therefore, for 0.16≤m≤0.17, we will have a stable solution that satisfies all traversability conditions.

Quasi-one-dimensional hydrogen bonding in nanoconfined ice

The Bernal-Fowler ice rules stipulate that each water molecule in an ice crystal should form four hydrogen bonds. However, in extreme or constrained conditions, the arrangement of water molecules deviates from conventional ice rules, resulting in properties significantly different from bulk water. In this study, we employ machine learning-driven first-principles simulations to identify a new stabilization mechanism in nanoconfined ice phases. Instead of forming four hydrogen bonds, nanoconfined crystalline ice can form a quasi-one-dimensional hydrogen-bonded structure that exhibits only two hydrogen bonds per water molecule. These structures consist of strongly hydrogen-bonded linear chains of water molecules that zig-zag along one dimension, stabilized by van der Waals interactions that stack these chains along the other dimension. The unusual interplay of hydrogen bonding and van der Waals interactions in nanoconfined ice results in atypical proton behavior such as potential ferroelectric behavior, low dielectric response, and long-range proton dynamics.

Unveiling the thermodynamic landscape of liquid Ti–Al–Ni alloys through first-principles simulations

We conducted ab initio molecular dynamics simulations to systematically examine the composition-dependent thermodynamic properties and atomic-scale interactions in liquid Ti–Al–Ni alloys throughout the entire ternary phase space at 2033 K. The calculated enthalpies of mixing demonstrated exothermic tendencies, with a distinct minimum in the composition of Ti0.0Al0.50Ni0.50, indicating significant Al–Ni attractive interactions. Incorporating ternary interaction parameters into the Redlich-Kister-Muggianu equation enabled accurate modeling of the complex variations in mixing enthalpy. Analysis of partial pair correlation functions and structure factors revealed chemical and topological short-range ordering (SRO), as well as medium-range ordering, within the liquid alloy. Quantifying deviations from ideal configurational entropy clarifies the coupling between chemical SRO and topological SRO, significantly impacting the overall Gibbs energy of mixing. This comprehensive atomistic study provides insights into the thermodynamics of Ti–Al–Ni alloys, paving the way for tailoring their properties for high-performance applications.

Impact of Fe-impurity centers on phonon subsystem of wurtzite-type ZnO

The paper addresses the question of the structural and vibrational properties of Fe-doped ZnO in the wurtzite structure with a lattice without an inversion center. The ZnO crystals containing Fe impurities in different charged states are studied by means of density functional theory (DFT) and potential-based methods. A first-principles simulation is performed to determine the local atomic configurations near the considered defects. The DFT results are compared with those obtained using the shell model. Both approaches give a similar pattern of lattice distortion around the Fe-impurity centers occupying cation sites in the isoelectronic charge state Fe2＋ and single-positive-charge state Fe3＋. The phonon local symmetrized densities of states projected onto the displacement of ions surrounding the defects are calculated by a well-established recursion method. The frequencies of defect vibrations of various symmetry types induced by Fe impurities are determined. The calculations made it possible to interpret the structure of the phonon sideband accompanying the zero-phonon line in polarized emission spectra attributed to the Fe3＋ intracenter transitions, as well as to estimate the role of Fe ions in the formation of observed peaks.

Exploring the Premelting Transition through Molecular Simulations Powered by Neural Network Potentials

The premelting layer on crystal surfaces significantly affects the stability, surface reactivity, and phase transition behaviors of crystals. Traditional methods for studying this layer—experimental techniques, classical simulations, and even first-principle simulations—have significant limitations in accuracy and scalability. To overcome these challenges, we employ molecular dynamic simulations based on neural network potentials to investigate the structural and dynamic behavior of the premelting layer on ice. This approach matches the accuracy of first-principle calculations while greatly improving computational efficiency, allowing us to simulate the ice–vapor interface on a much larger scale. In this study, we conducted a one-nanosecond simulation of the ice–vapor interface involving 1024 water molecules. This significantly exceeds the time and size scales of previous first-principle studies. Our simulation results indicate complete surface melting. Furthermore, our simulation results reveal dynamic heterogeneity within the premelting layer, with molecules segregated into clusters of low and high mobility.

DFT study of Cun (n = 1–3) cluster-modified WSe2 monolayers for the detection of SF6 decomposition gases (H2S, SO2, SOF2 and SO2F2)

The role of SF6 in gas-insulated equipment is crucial for insulation and arc extinction. When subjected to electrical faults, thermal faults, and mechanical failures in insulation devices, SF6 can decompose into H2S, SO2, SOF2, and SO2F2. This study conducted first-principles simulations to analyze the effect of Cun (n = 1–3) cluster-modified monolayer WSe2 on sensing H2S, SO2, SOF2, and SO2F2 gases during SF6 decomposition. The optimal doping positions of Cun-WSe2 clusters at n = 1, 2, and 3 were determined, showcasing their superiority over pure WSe2 in terms of band gap, frontier orbitals, and density of states. Subsequently, a detailed investigation was carried out on the adsorption effects of the four gases at the optimal doping positions, including parameters such as adsorption distance, adsorption energy, charge transfer, differential charge density, and density of states. It was found that when the number of copper atoms in the cluster increased to 3, the banding energy sharply rose to -2.395 eV. Simulation results demonstrated the adsorption behavior of H2S on Cun (n = 1–3)-WSe2 demonstrates remarkable affinity, with an increasing adsorption energy as the number of Cu atoms rises. Notably, Cun (n = 1–3)-WSe2 exhibits favorable desorption times for SO2. At 378 K, the desorption time for SO2@Cu3-WSe2 is 14.7 s. At 498 K, desorption times for SO2@Cu1-WSe2 and SO2@Cu2-WSe2 are 7.59 s and 2.85 s, respectively. When the number of copper atoms is 2, the cluster-modified system desorbs SOF2 at room temperature in only 0.89 s. Moreover, Cun (n = 1–3)-WSe2 displays strong adsorption towards SO2F2, characterized by prolonged desorption times, rendering it a promising adsorbent for SO2F2 removal. This study aims to highlight the adsorption effects of different numbers of Cu atomic clusters in the Cun-WSe2 system on SF6 decomposition gas, further advancing research for developing high-performance SF6 decomposition gas sensors.

Reactant Discovery with an Ab Initio Nanoreactor: Exploration of Astrophysical N-Heterocycle Precursors and Formation Pathways.

The incorporation of nitrogen atoms into cyclic compounds is essential for terrestrial life; nitrogen-containing (N-)heterocycles make up DNA and RNA nucleobases, several amino acids, B vitamins, porphyrins, and other components of biomolecules. The discovery of these molecules on meteorites with non-terrestrial isotopic abundances supports the hypothesis of exogenous delivery of prebiotic material to early Earth; however, there has been no detection of these species in interstellar environments, indicating that there is a need for greater knowledge of their astrochemical formation and destruction pathways. Here, we present results of simulations of gas-phase pyrrole and pyridine formation from an ab initio nanoreactor, a first-principles molecular dynamics simulation method that accelerates reaction discovery by applying non-equilibrium forces that are agnostic to individual reaction coordinates. Using the nanoreactor in a retrosynthetic mode, starting with the N-heterocycle of interest and a radical leaving group, then considering the discovered reaction pathways in reverse, a rich landscape of N-heterocycle-forming reactivity can be found. Several of these reaction pathways, when mapped to their corresponding minimum energy paths, correspond to novel barrierless formation pathways for pyridine and pyrrole, starting from both detected and hypothesized astrochemical precursors. This study demonstrates how first-principles reaction discovery can build mechanistic knowledge in astrochemical environments as well as in early Earth models such as Titan's atmosphere where N-heterocycles have been tentatively detected.

(Invited) Computational Design and Analysis of Novel Battery Electrolytes Driven by the Grotthuss Mechanism

Candidate systems for next-generation electrolyte materials, such as deep eutectic solvents and ionic liquids, often suffer from high viscosities, which suppresses rates of charge transport and limits their performance characteristics. A strategy for circumventing this problem is to leverage the structural or Grotthuss mechanism of proton transport through hydrogen-bond networks, which can exhibit high proton diffusion rates even when rates of vehicular charge transport are poor. In this talk, I will describe a project aimed at leveraging computational design and simulation approaches, in combination with experimental synthesis and characterization, to develop a novel class of battery electrolytes based on the structural/Grotthuss diffusion mechanism. The workflow involves identification of a suitable proton-carrier liquid, a proton source, and a redox-active species capable of undergoing proton-coupled electron transfer (PCET) reactions. I will discuss the computational methods, which involve a combination of machine learning and first-principles simulation techniques, candidate chemical species for each of the components, first simulation and experimental protocols for combining these components into a high-performance electrolyte, preliminary results, and next steps in the evolution of the project. This work will serve to illustrate both the power of modern computational approaches in the design of electrochemical systems but also to broaden the perspective on what constitutes a “breakthrough” electrolyte. Figure 1