Heterocycle- and Amine-Free Electrochromic and Electrofluorochromic Molecules for Energy-Saving See-Through Smart Windows and Displays.

Electrochromic (EC) smart windows are an elegant alternative to dusty curtains, blinds, and traditional dimming devices. The EC energy storage smart windows and displays received remarkable attention in the optoelectronic industry as they hold promise for high energy efficiency, low power consumption, reversibility, and swift response to stimuli. However, achieving these properties remains challenging. Moreover, most EC molecules do not exhibit electrofluorochromism, which is highly essential for smart displays because its EC property can modulate the solar heat entering the building, and its electrofluorochromic (EFC) aspects can create lighting during the night. In this work, a structure-property relationship is utilized to develop new electrochromes that can store the injected charge, and these molecules indeed exhibit electrofluorochromism. The compounds are synthesized from tetrabenzofluorene with two aromatic acceptor units, and avoids the use of widely studied heterocycles and amine derivatives. The electrochromes switches from yellow to dark hue in solution, solid, and gel state. The compounds display exceptional electrochemical stability and reversibility in 1000 cycles and capacity retention of 93-100 % in 300 charging-discharging cycles. The proof-of-concept device fabrication of the self-dimming EC smart window presented here demonstrates that it can furnish visual comfort, modulate transmitted light and glare, and reduce energy usage.

Capillary Condensation of Water in Graphene Nanocapillaries.

Recent experiments have revealed that the macroscopic Kelvin equation remains surprisingly accurate even for nanoscale capillaries. This phenomenon was so far explained by the oscillatory behavior of the solid-liquid interfacial free energy. We here demonstrate thermodynamic and capillarity inconsistencies with this explanation. After revising the Kelvin equation, we ascribe its validity at nanoscale confinement to the effect of disjoining pressure. To substantiate our hypothesis, we employed molecular dynamics simulations to evaluate interfacial heat transfer and wetting properties. Our assessments unveil a breakdown in a previously established proportionality between the work of adhesion and the Kapitza conductance at capillary heights below 1.3 nm, where the dominance of the work of adhesion shifts primarily from energy to entropy. Alternatively, the peak density of the initial water layer can effectively probe the work of adhesion. Unlike under bulk conditions, high confinement renders the work of adhesion entropically unfavorable.

Reduction-enhanced water flux through layered graphene oxide (GO) membranes stabilized with H3O+ and OH- ions.

Graphene oxide (GO) is one of the most promising candidates for next generation of atomically thin membranes. Nevertheless, one of the major issues for real world application of GO membranes is their undesirable swelling in an aqueous environment. Recently, we demonstrated that generation of H3O+ and OH- ions (e.g., with an external electric field) in the interlayer gallery could impart aqueous stability to the layered GO membranes (A. Gogoi, ACS Appl. Mater. Interfaces, 2022, 14, 34946). This, however, compromises the water flux through the membrane. In this study, we report on reducing the GO nanosheets as a solution to this issue. With the reduction of the GO nanosheets, the water flux through the layered GO membrane initially increases and then decreases again beyond a certain degree of reduction. Here, two key factors are at play. Firstly, the instability of the H-bond network between water molecules and the GO nanosheets, which increases the water flux. Secondly, the pore size reduction in the interlayer gallery of the membranes, which decreases the water flux. We also observe a significant improvement in the salt rejection of the membranes, due to the dissociation of water molecules in the interlayer gallery. In particular, for the case of 10% water dissociation, the water flux through the membranes can be enhanced without altering its selectivity. This is an encouraging observation as it breaks the traditional tradeoff between water flux and salt rejection of a membrane.

Combined First-Principles and Experimental Study on the Microstructure and Mechanical Characteristics of the Multicomponent Additive-Manufactured Ti-35Nb-7Zr-5Ta Alloy.

New ß-stabilized Ti-based alloys are highly promising for bone implants, thanks in part to their low elasticity. The nature of this elasticity, however, is as yet unknown. We here present combined first-principles DFT calculations and experiments on the microstructure, structural stability, mechanical characteristics, and electronic structure to elucidate this origin. Our results suggest that the studied ß Ti-35Nb-7Zr-5Ta wt % (TNZT) alloy manufactured by the electron-beam powder bed fusion (E-PBF) method has homogeneous mechanical properties (H = 2.01 ± 0.22 GPa and E = 69.48 ± 0.03 GPa) along the building direction, which is dictated by the crystallographic texture and microstructure morphologies. The analysis of the structural and electronic properties, as the main factors dominating the chemical bonding mechanism, indicates that TNZT has a mixture of strong metallic and weak covalent bonding. Our calculations demonstrate that the softening in the Cauchy pressure (C' = 98.00 GPa) and elastic constant C̅44 = 23.84 GPa is the origin of the low elasticity of TNZT. Moreover, the nature of this softening phenomenon can be related to the weakness of the second and third neighbor bonds in comparison with the first neighbor bonds in the TNZT. Thus, the obtained results indicate that a carefully designed TNZT alloy can be an excellent candidate for the manufacturing of orthopedic internal fixation devices. In addition, the current findings can be used as guidance not only for predicting the mechanical properties but also the nature of elastic characteristics of the newly developed alloys with yet unknown properties.

Cation-controlled permeation of charged polymers through nanocapillaries.

Molecular dynamics simulations are used to study the effects of different cations on the permeation of charged polymers through flat capillaries with heights below 2 nm. Interestingly, we found that, despite being monovalent, Li^{+}, Na^{+}, and K^{+} cations have different effects on polymer permeation, which consequently affects their transmission speed throughout those capillaries. We attribute this phenomenon to the interplay of the cations' hydration free energies and the hydrodynamic drag in front of the polymer when it enters the capillary. Different alkali cations exhibit different surface versus bulk preferences in small clusters of water under the influence of an external electric field. This paper presents a tool to control the speed of charged polymers in confined spaces using cations.

Extending and validating bubble nucleation rate predictions in a Lennard-Jones fluid with enhanced sampling methods and transition state theory.

We calculate bubble nucleation rates in a Lennard-Jones fluid through explicit molecular dynamics simulations. Our approach-based on a recent free energy method (dubbed reweighted Jarzynski sampling), transition state theory, and a simple recrossing correction-allows us to probe a fairly wide range of rates in several superheated and cavitation regimes in a consistent manner. Rate predictions from this approach bridge disparate independent literature studies on the same model system. As such, we find that rate predictions based on classical nucleation theory, direct brute force molecular dynamics simulations, and seeding are consistent with our approach and one another. Published rates derived from forward flux sampling simulations are, however, found to be outliers. This study serves two purposes: First, we validate the reliability of common modeling techniques and extrapolation approaches on a paradigmatic problem in materials science and chemical physics. Second, we further test our highly generic recipe for rate calculations, and establish its applicability to nucleation processes.

Arresting Aqueous Swelling of Layered Graphene-Oxide Membranes with H3O+ and OH- Ions.

Over the past decade, graphene oxide (GO) has emerged as a promising membrane material with superior separation performance and intriguing mechanical/chemical stability. However, its practical implementation remains very challenging primarily because of its undesirable swelling in an aqueous environment. Here, we demonstrated that dissociation of water molecules into H3O+ and OH- ions inside the interlayer gallery of a layered GO membrane can strongly affect its stability and performance. We reveal that H3O+ and OH- ions form clusters inside the GO laminates that impede the permeance of water and salt ions through the membrane. Dynamics of those clusters is sensitive to an external ac electric field, which can be used to tailor the membrane performance. The presence of H3O+ and OH- ions also leads to increased stability of the hydrogen bond (H-bond) network among the water molecules and the GO layers, which further reduces water permeance through the membrane, while crucially imparting stability to the layered GO membrane against undesirable swelling.

Distribution Pattern of Metal Atoms in Bimetal-Doped Pyridinic-N4 Pores Determines Their Potential for Electrocatalytic N2 Reduction.

Doping two single transition-metal (TM) atoms on a substrate host opens numerous possibilities for catalyst design. However, what if the substrate contains more than one vacancy site? Then, the combination of two TMs along with their distribution patterns becomes a design parameter potentially complementary to the substrate itself and the bimetal composition. In this study, we investigate ammonia synthesis under mild electrocatalytic conditions on a transition-metal-doped porous C24N24 catalyst using density functional theory (DFT). The TMs studied include Ti, Mn, and Cu in a 2:4 dopant ratio (Ti2Mn4@C24N24 and Ti2Cu4@C24N24). Our computations show that a single Ti atom in both catalysts exhibits the highest selectivity for N2 fixation at ambient conditions. This work is a good theoretical model to establish the structure-activity relationship, and the knowledge earned from the metal-N4 moieties may help studies of related nanomaterials, especially those with curved structures.

Indentation of graphene nano-bubbles.

Molecular dynamics simulations are used to investigate the effect of an AFM tip when indenting graphene nano bubbles filled by a noble gas (i.e. He, Ne and Ar) up to the breaking point. The failure points resemble those of viral shells as described by the Föppl-von Kármán (FvK) dimensionless number defined in the context of elasticity theory of thin shells. At room temperature, He gas inside the bubbles is found to be in the liquid state while Ne and Ar atoms are in the solid state although the pressure inside the nano bubble is below the melting pressure of the bulk. The trapped gases are under higher hydrostatic pressure at low temperatures than at room temperature.

Breakdown of Universal Scaling for Nanometer-Sized Bubbles in Graphene.

We report the formation of nanobubbles on graphene with a radius of the order of 1 nm, using ultralow energy implantation of noble gas ions (He, Ne, Ar) into graphene grown on a Pt(111) surface. We show that the universal scaling of the aspect ratio, which has previously been established for larger bubbles, breaks down when the bubble radius approaches 1 nm, resulting in much larger aspect ratios. Moreover, we observe that the bubble stability and aspect ratio depend on the substrate onto which the graphene is grown (bubbles are stable for Pt but not for Cu) and trapped element. We interpret these dependencies in terms of the atomic compressibility of the noble gas as well as of the adhesion energies between graphene, the substrate, and trapped atoms.

Linking Bi-Metal Distribution Patterns in Porous Carbon Nitride Fullerene to Its Catalytic Activity toward Gas Adsorption.

Immobilization of two single transition metal (TM) atoms on a substrate host opens numerous possibilities for catalyst design. If the substrate contains more than one vacancy site, the combination of TMs along with their distribution patterns becomes a design parameter potentially complementary to the substrate itself and the bi-metal composition. By means of DFT calculations, we modeled three dissimilar bi-metal atoms (Ti, Mn, and Cu) doped into the six porphyrin-like cavities of porous C24N24 fullerene, considering different bi-metal distribution patterns for each binary complex, viz. TixCuz@C24N24, TixMny@C24N24, and MnyCuz@C24N24 (with x, y, z = 0-6). We elucidate whether controlling the distribution of bi-metal atoms into the C24N24 cavities can alter their catalytic activity toward CO2, NO2, H2, and N2 gas capture. Interestingly, Ti2Mn4@C24N24 and Ti2Cu4@C24N24 complexes showed the highest activity and selectively toward gas capture. Our findings provide useful information for further design of novel few-atom carbon-nitride-based catalysts.

Reaction mechanisms of C(3PJ) and C+(2PJ) with benzene in the interstellar medium from quantum mechanical molecular dynamics simulations.

While spectroscopic data on small hydrocarbons in interstellar media in combination with crossed molecular beam (CMB) experiments have provided a wealth of information on astrochemically relevant species, much of the underlying mechanistic pathways of their formation remain elusive. Therefore, in this work, the chemical reaction mechanisms of C(3PJ) + C6H6 and C+(2P) + C6H6 systems using the quantum mechanical molecular dynamics (QMMD) technique at the PBE0-D3(BJ) level of theory is investigated, mimicking a CMB experiment. Both the dynamics of the reactions as well as the electronic structure for the purpose of the reaction network are evaluated. The method is validated for the first reaction by comparison to the available experimental data. The reaction scheme for the C(3PJ) + C6H6 system covers the literature data, e.g. the major products are the 1,2-didehydrocycloheptatrienyl radical (C7H5) and benzocyclopropenyl radical (C6H5-CH), and it reveals the existence of less common pathways for the first time. The chemistry of the C+(2PJ) + C6H6 system is found to be much richer, and we have found that this is because of more exothermic reactions in this system in comparison to those in the C(3PJ) + C6H6 system. Moreover, using the QMMD simulation, a number of reaction paths have been revealed that produce three distinct classes of reaction products with different ring sizes. All in all, at all the collision energies and orientations, the major product is the heptagon molecular ion for the ionic system. It is also revealed that the collision orientation has a dominant effect on the reaction products in both systems, while the collision energy mostly affects the charged system. These simulations both prove the applicability of this approach to simulate crossed molecular beams, and provide fundamental information on reactions relevant for the interstellar medium.

Free energy barriers from biased molecular dynamics simulations.

Atomistic simulation methods for the quantification of free energies are in wide use. These methods operate by sampling the probability density of a system along a small set of suitable collective variables (CVs), which is, in turn, expressed in the form of a free energy surface (FES). This definition of the FES can capture the relative stability of metastable states but not that of the transition state because the barrier height is not invariant to the choice of CVs. Free energy barriers therefore cannot be consistently computed from the FES. Here, we present a simple approach to calculate the gauge correction necessary to eliminate this inconsistency. Using our procedure, the standard FES as well as its gauge-corrected counterpart can be obtained by reweighing the same simulated trajectory at little additional cost. We apply the method to a number of systems-a particle solvated in a Lennard-Jones fluid, a Diels-Alder reaction, and crystallization of liquid sodium-to demonstrate its ability to produce consistent free energy barriers that correctly capture the kinetics of chemical or physical transformations, and discuss the additional demands it puts on the chosen CVs. Because the FES can be converged at relatively short (sub-ns) time scales, a free energy-based description of reaction kinetics is a particularly attractive option to study chemical processes at more expensive quantum mechanical levels of theory.

Modeling the Physicochemical Properties of Natural Deep Eutectic Solvents.

Natural deep eutectic solvents (NADES) are mixtures of naturally derived compounds with a significantly decreased melting point owing to specific interactions among the constituents. NADES have benign properties (low volatility, flammability, toxicity, cost) and tailorable physicochemical properties (by altering the type and molar ratio of constituents); hence, they are often considered to be a green alternative to common organic solvents. Modeling the relation between their composition and properties is crucial though, both for understanding and predicting their behavior. Several efforts have been made to this end. This Review aims at structuring the present knowledge as an outline for future research. First, the key properties of NADES are reviewed and related to their structure on the basis of the available experimental data. Second, available modeling methods applicable to NADES are reviewed. At the molecular level, DFT and molecular dynamics allow density differences and vibrational spectra to be interpreted, and interaction energies to be computed. Additionally, properties at the level of the bulk medium can be explained and predicted by semi-empirical methods based on ab initio methods (COSMO-RS) and equation of state models (PC-SAFT). Finally, methods based on large datasets are discussed: models based on group-contribution methods and machine learning. A combination of bulk-medium and dataset modeling allows qualitative prediction and interpretation of phase equilibria properties on the one hand, and quantitative prediction of melting point, density, viscosity, surface tension, and refractive index on the other. Multiscale modeling, combining molecular and macroscale methods, is expected to strongly enhance the predictability of NADES properties and their interaction with solutes, and thus yield truly tailorable solvents to accommodate (bio)chemical reactions.

Effect of van der Waals interactions on the adhesion strength at the interface of the hydroxyapatite-titanium biocomposite: a first-principles study.

Hydroxyapatite (HAP) is frequently used as biocompatible coating on Ti-based implants. In this context, the HAP-Ti adhesion is of crucial importance. Here, we report ab initio calculations to investigate the influence of Si incorporation into the amorphous calcium-phosphate (a-HAP) structure on the interfacial bonding mechanism between the a-HAP coating and an amorphous titanium dioxide (a-TiO2) substrate, contrasting two different density functionals: PBE-GGA, and DFT-D3, which are capable of describing the influence of the van der Waals (vdW) interactions. In particular, we discuss the effect of dispersion on the work of adhesion (W ad), equilibrium geometries, and charge density difference (CDD). We find that replacement of P by Si in a-HAP (a-Si-HAP) with the creation of OH vacancies as charge compensation results in a significant increase in the bond strength between the coating and substrate in the case of using the PBE-GGA functional. However, including the vdW interactions shows that these forces considerably contribute to the W ad. We show that the difference (W ad - W ad(vdW)) is on average more than 1.1 J m-2 and 0.5 J m-2 for a-HAP/a-TiO2 and a-Si-HAP/a-TiO2, respectively. These results reveal that including vdW interactions is essential for accurately describing the chemical bonding at the a-HAP/a-TiO2 interface.

Ensemble-Based Molecular Simulation of Chemical Reactions under Vibrational Nonequilibrium.

We present an approach to incorporate the effect of vibrational nonequilibrium in molecular dynamics (MD) simulations. A perturbed canonical ensemble, in which selected modes are excited to higher temperature while all others remain equilibrated at low temperature, is simulated by applying a specifically tailored bias potential. Our method can be readily applied to any (classical or quantum mechanical) MD setup at virtually no additional computational cost and allows the study of reactions of vibrationally excited molecules in nonequilibrium environments such as plasmas. In combination with enhanced sampling methods, the vibrational efficacy and mode selectivity of vibrationally stimulated reactions can then be quantified in terms of chemically relevant observables, such as reaction rates and apparent free energy barriers. We first validate our method for the prototypical hydrogen exchange reaction and then show how it can capture the effect of vibrational excitation on a symmetric SN2 reaction and radical addition on CO2.

Modelling molecular adsorption on charged or polarized surfaces: a critical flaw in common approaches.

A number of recent computational material design studies based on density functional theory (DFT) calculations have put forward a new class of materials with electrically switchable chemical characteristics that can be exploited in the development of tunable gas storage and electrocatalytic applications. We find systematic flaws in almost every computational study of gas adsorption on polarized or charged surfaces, stemming from an improper and unreproducible treatment of periodicity, leading to very large errors of up to 3 eV in some cases. Two simple corrective procedures that lead to consistent results are proposed, constituting a crucial course correction to the research in the field.

A first principles study of p-type defects in LaCrO3.

Recently, Sr-doped LaCrO3 has been experimentally introduced as a new p-type transparent conducting oxide. It is demonstrated that substituting Sr for La results in inducing p-type conductivity in LaCrO3. Performing first principles calculations we study the electronic structure and formation energy of various point defects in LaCrO3. Our results for the formation energies show that in addition to Sr, two more divalent defects, Ca and Ba, substituting for La in LaCrO3, behave as shallow acceptors in line with previous experimental reports. We further demonstrate that under oxygen-poor growth conditions, these shallow acceptors will be compensated by intrinsic donor-like defects (an oxygen vacancy and Cr on an oxygen site), but in the oxygen-rich growth regime the shallow acceptors have the lowest formation energies between all considered defects and will lead to p-type conductivity.

A DFT study of H-dissolution into the bulk of a crystalline Ni(111) surface: a chemical identifier for the reaction kinetics.

In this study, we investigated the diffusion of H-atoms to the subsurface and their further diffusion into the bulk of a Ni(111) crystal by means of density functional theory calculations in the context of thermal and plasma-assisted catalysis. The H-atoms at the surface can originate from the dissociative adsorption of H2 or CH4 molecules, determining the surface H-coverage. When a threshold H-coverage is passed, corresponding to 1.00 ML for the crystalline Ni(111) surface, the surface-bound H-atoms start to diffuse to the subsurface. A similar threshold coverage is observed for the interstitial H-coverage. Once the interstitial sites are filled up with a coverage above 1.00 ML of H, dissolution of interstitial H-atoms to the layer below the interstitial sites will be initiated. Hence, by applying a high pressure or inducing a reactive plasma and high temperature, increasing the H-flux to the surface, a large amount of hydrogen can diffuse in a crystalline metal like Ni and can be absorbed. The formation of metal hydride may modify the entire reaction kinetics of the system. Equivalently, the H-atoms in the bulk can easily go back to the surface and release a large amount of heat. In a plasma process, H-atoms are formed in the plasma, and therefore the energy barrier for dissociative adsorption is dismissed, thus allowing achievement of the threshold coverage without applying a high pressure as in a thermal process. As a result, depending on the crystal plane and type of metal, a large number of H-atoms can be dissolved (absorbed) in the metal catalyst, explaining the high efficiency of plasma-assisted catalytic reactions. Here, the mechanism of H-dissolution is established as a chemical identifier for the investigation of the reaction kinetics of a chemical process.

Toward the Understanding of Selective Si Nano-Oxidation by Atomic Scale Simulations.

The continuous miniaturization of nanodevices, such as transistors, solar cells, and optical fibers, requires the controlled synthesis of (ultra)thin gate oxides (<10 nm), including Si gate-oxide (SiO2) with high quality at the atomic scale. Traditional thermal growth of SiO2 on planar Si surfaces, however, does not allow one to obtain such ultrathin oxide due to either the high oxygen diffusivity at high temperature or the very low sticking ability of incident oxygen at low temperature. Two recent techniques, both operative at low (room) temperature, have been put forward to overcome these obstacles: (i) hyperthermal oxidation of planar Si surfaces and (ii) thermal or plasma-assisted oxidation of nonplanar Si surfaces, including Si nanowires (SiNWs). These nano-oxidation processes are, however, often difficult to study experimentally, due to the key intermediate processes taking place on the nanosecond time scale. In this Account, these Si nano-oxidation techniques are discussed from a computational point of view and compared to both hyperthermal and thermal oxidation experiments, as well as to well-known models of thermal oxidation, including the Deal-Grove, Cabrera-Mott, and Kao models and several alternative mechanisms. In our studies, we use reactive molecular dynamics (MD) and hybrid MD/Monte Carlo simulation techniques, applying the Reax force field. The incident energy of oxygen species is chosen in the range of 1-5 eV in hyperthermal oxidation of planar Si surfaces in order to prevent energy-induced damage. It turns out that hyperthermal growth allows for two growth modes, where the ultrathin oxide thickness depends on either (1) only the kinetic energy of the incident oxygen species at a growth temperature below Ttrans = 600 K, or (2) both the incident energy and the growth temperature at a growth temperature above Ttrans. These modes are specific to such ultrathin oxides, and are not observed in traditional thermal oxidation, nor theoretically considered by already existing models. In the case of thermal or plasma-assisted oxidation of small Si nanowires, on the other hand, the thickness of the ultrathin oxide is a function of the growth temperature and the nanowire diameter. Below Ttrans, which varies with the nanowire diameter, partially oxidized SiNW are formed, whereas complete oxidation to a SiO2 nanowire occurs only above Ttrans. In both nano-oxidation processes at lower temperature (T < Ttrans), final sandwich c-Si|SiOx|a-SiO2 structures are obtained due to a competition between overcoming the energy barrier to penetrate into Si subsurface layers and the compressive stress (∼2-3 GPa) at the Si crystal/oxide interface. The overall atomic-simulation results strongly indicate that the thickness of the intermediate SiOx (x < 2) region is very limited (∼0.5 nm) and constant irrespective of oxidation parameters. Thus, control over the ultrathin SiO2 thickness with good quality is indeed possible by accurately tuning the oxidant energy, oxidation temperature and surface curvature. In general, we discuss and put in perspective these two oxidation mechanisms for obtaining controllable ultrathin gate-oxide films, offering a new route toward the fabrication of nanodevices via selective nano-oxidation.