Plasma Catalysis Modeling: How Ideal Is Atomic Hydrogen for Eley-Rideal?

Plasma catalysis is an emerging technology, but a lot of questions about the underlying surface mechanisms remain unanswered. One of these questions is how important Eley-Rideal (ER) reactions are, next to Langmuir-Hinshelwood reactions. Most plasma catalysis kinetic models predict ER reactions to be important and sometimes even vital for the surface chemistry.

Improving Molecule-Metal Surface Reaction Networks Using the Meta-Generalized Gradient Approximation: CO Hydrogenation.

Density functional theory is widely used to gain insights into molecule-metal surface reaction networks, which is important for a better understanding of catalysis. However, it is well-known that generalized gradient approximation (GGA) density functionals (DFs), most often used for the study of reaction networks, struggle to correctly describe both gas-phase molecules and metal surfaces. Also, GGA DFs typically underestimate reaction barriers due to an underestimation of the self-interaction energy.

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.

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.

Reduction-enhanced water flux through layered graphene oxide (GO) membranes stabilized with HO 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 HO and OH ions (, with an external electric field) in the interlayer gallery could impart aqueous stability to the layered GO membranes (A.

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

New β-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.

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.

Clogging and Unclogging of Hydrocarbon-Contaminated Nanochannels.

The recent advantages of the fabrication of artificial nanochannels enabled new research on the molecular transport, permeance, and selectivity of various gases and molecules. However, the physisorption/chemisorption of the unwanted molecules (usually hydrocarbons) inside nanochannels results in the alteration of the functionality of the nanochannels. We investigated contamination due to hydrocarbon molecules, nanochannels made of graphene, hexagonal boron nitride, BCN, and molybdenum disulfide using molecular dynamics simulations.

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.

Arresting Aqueous Swelling of Layered Graphene-Oxide Membranes with HO 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 HO and OH ions inside the interlayer gallery of a layered GO membrane can strongly affect its stability and performance.

Distribution Pattern of Metal Atoms in Bimetal-Doped Pyridinic-N Pores Determines Their Potential for Electrocatalytic N 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 CN catalyst using density functional theory (DFT).

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 ( 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.

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.

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 CN fullerene, considering different bi-metal distribution patterns for each binary complex, TiCu@CN, TiMn@CN, and MnCu@CN (with x, y, z = 0-6).

Reaction mechanisms of C(P) and C(P) 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.

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 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-TiO) 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.

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.

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.

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.

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.

Atomistic simulations of graphite etching at realistic time scales.

Hydrogen-graphite interactions are relevant to a wide variety of applications, ranging from astrophysics to fusion devices and nano-electronics. In order to shed light on these interactions, atomistic simulation using Molecular Dynamics (MD) has been shown to be an invaluable tool. It suffers, however, from severe time-scale limitations.

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

Recently, Sr-doped LaCrO 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 LaCrO. Performing first principles calculations we study the electronic structure and formation energy of various point defects in LaCrO.

Effect of head group and lipid tail oxidation in the cell membrane revealed through integrated simulations and experiments.

We report on multi-level atomistic simulations for the interaction of reactive oxygen species (ROS) with the head groups of the phospholipid bilayer, and the subsequent effect of head group and lipid tail oxidation on the structural and dynamic properties of the cell membrane. Our simulations are validated by experiments using a cold atmospheric plasma as external ROS source. We found that plasma treatment leads to a slight initial rise in membrane rigidity, followed by a strong and persistent increase in fluidity, indicating a drop in lipid order.

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 H or CH molecules, determining the surface H-coverage. When a threshold H-coverage is passed, corresponding to 1.

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 (SiO) with high quality at the atomic scale. Traditional thermal growth of SiO 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).