Long-range Van Der Waals Interactions Research Articles

Highly sensitive sensing of CO and HF gases by monolayer CuCl.

Using a first-principles approach, the adsorption characteristics of CO and HF on a CuCl monolayer (ML) are studied with Grimme-scheme DFT-D2 for accurate description of the long-range (van der Waals) interactions. According to our study, CO gas molecules undergo chemisorption and HF gas molecules show a physisorption phenomenon on the CuCl monolayer. The adsorption energy for CO is -1.80 eV, which is quite a large negative value compared to that on other previously studied substrates, like InN (-0.223 eV), phosphorene (0.325 eV), Janus Te2Se (-0.171 eV), graphene (P-graphene, -0.12 eV, B-graphene, -0.14 eV, N-graphene, -0.1 eV) and monolayer ZnS (-0.96 eV), as well as pristine hBN (0.21 eV) and Ti-doped hBN (1.66 eV). Meanwhile, for HF, the adsorption energy value is -0.31 eV (greater than that of Ti-doped hBN, 0.27 eV). For CO, the large value of the diffusion energy barrier (DEB = 1.26 eV) during its movement between two optimal sites indicates that clustering can be prevented if many molecules of CO are adsorbed on the CuCl ML. For HF, the value of the DEB (0.082 eV) implies that the adsorption phenomenon may happen quite easily upon the CuCl ML. The transfer of charge according to Bader charge analysis and the variation in the work function depend only on the properties of the elements involved, i.e., their nature, rather than the local binding environment. The work function and band-gap energy variation of the CuCl ML (before and after adsorption) show high sensitivity and selectivity of CO and HF binding with the CuCl monolayer. HF molecules give a more rapid recovery time of 1.09 × 10-7 s compared to that of CO molecules at a room temperature (RT) of 300 K, which indicates that the necessary adsorption and reusability of the CuCl ML for HF can be accomplished effectively at RT. Significant changes in the conductivity are observed due to the CO adsorption at various temperatures, as compared to adsorption of HF, which suggests the possibility of a modification in the conductivity of the CuCl ML.

Structural, electronic and magnetic properties of greigite Fe3S4 by GGA and GGA+U versus SCAN meta-GGA density functionals

The performance of exchange-correlation functional of density functional theory represented in generalized gradient approximation (GGA) and in the strongly constrained and appropriately normed (SCAN) meta-GGA scheme to study structural, electronic, and magnetic properties of greigite (Fe3S4) was investigated. The effects of inclusion of strong electron correlations represented by on-site Hubbard correction U, and nonlocality of the long-range van der Waals (vdW) interactions were also considered. Geometry optimization yielded the inverse spinel structure and lattice parameter of greigite in good agreement with experimental data. Calculated electronic structure revealed a half-metallic nature of the greigite bands for the applied functionals except for GGA, which predicts metallic behavior. Antiferromagnetic coupling of iron ions in tetrahedral and octahedral coordinations makes the overall crystal structure ferrimagnetic. In general the GGA+U and SCAN show comparable performance in prediction physical properties of greigite. Inclusion of the vdW correction does not change the character of the bands.

Insights on the chloride adsorption stability in cement mortar under current field and sulfate attack: From experiments to molecular dynamics simulation

The destabilization together with boundary chloride ions releasing leads to the corrosion of steel bars, posing nonnegligible risks to the durability of structures. This work attempted to design the typical pore solution of underground constructions via methods of combining NaCl with Na2SO4 along with conducting a stray current continuously. The bound chloride stability of mortar under the action of electric current was systematically determined. The reaction mechanisms were tested by quantitative XRD, TG-DTG, FTIR, FESEM, and X-CT. Molecular dynamics was utilized to simulate the physical binding processes of C–S–H of Cl−/SO42- and their interaction under the actions of electric field by comparing the ions displacement trajectory, radial distribution function, and moving ability. The experimental results showed that the SO42- weakened the chemical chloride binding capacity with the Friedel's salt, portlandite, and calcium silicate decomposed to produce gypsum or ettringite. The electric field demonstrated less impact on the stabilities of chemical-bound Cl−, but promoted SO42- redistributions, causing substantial pore coarsening. The simulation revealed that the physical binding contained short-range ion Coulomb-interactions and long-range van der Waals interactions. The SO42- inhibited the binding of the C–S–H on Cl− by fact that the deposition large cluster of Na–SO4 blocked the nano-meter channels and competitive adsorption occurred at the SiOCa+ sites, while the introduction of electric field weakened the dominating effects of Coulomb-interactions and improved the ions desorption gradually. Hopefully, the transport and adsorption mechanisms of the Cl− in the cement-based materials can help guide the underground concrete with durability.

Quantum mechanics based non-bonded force field functions for use in molecular dynamics simulations of materials and systems: The nitrogen and oxygen columns.

Accurate Force Fields (FFs) are essential for Molecular Dynamics (MD) simulations of the dynamics of realistic materials in terms of atomic-level interactions. The FF parameters of short-range valence interactions can be derived through Quantum Mechanical (QM) calculations on model systems practical for QM (<300 atoms). Similarly, the dynamic electrostatic interactions can be described with methods such as QEq or PQEq that allow charges and polarization to adjust dynamically. However, accurately extracting long-range van der Waals (vdW) interactions from QM calculations poses challenges due to the absence of a definitive method to distinguish between the different energetic components of electrostatics, polarization, vdW, hydrogen bonding, and valence interactions. To do this we use the Perdew-Burke-Ernzerhof flavor of Density Functional Theory, including empirical D3 vdW corrections, to predict the Equation of State for each element (keeping any covalent bonds fixed), from which we obtain the two-body vdW nonbond potential. Here, we extend these calculations to include non-bonded parameters for the N and O columns of the periodic table so that we now describe columns 15 (N), 16 (O), 17 (F), and 18 (Ne) of the periodic table. For these 20 elements, we find that the two-body vdW potentials can all be mapped to a single universal two-body curve, with just three scaling parameters: Re, De, and L. We refer to this as the Universal NonBond (UNB) potential. We expect this to be useful for new MD simulations and a helpful starting point to obtain UNB parameters for the remainder of the periodic table.

Highly-excited Rydberg excitons in synthetic thin-film cuprous oxide

Cuprous oxide (hbox {Cu}{}_2hbox {O}) has recently emerged as a promising material in solid-state quantum technology, specifically for its excitonic Rydberg states characterized by large principal quantum numbers (n). The significant wavefunction size of these highly-excited states (proportional to n^2) enables strong long-range dipole-dipole (proportional to n^4) and van der Waals interactions (proportional to n^{11}). Currently, the highest-lying Rydberg states are found in naturally occurring hbox {Cu}_2hbox {O}. However, for technological applications, the ability to grow high-quality synthetic samples is essential. The fabrication of thin-film hbox {Cu}{}_2hbox {O} samples is of particular interest as they hold potential for observing extreme single-photon nonlinearities through the Rydberg blockade. Nevertheless, due to the susceptibility of high-lying states to charged impurities, growing synthetic samples of sufficient quality poses a substantial challenge. This study successfully demonstrates the CMOS-compatible synthesis of a hbox {Cu}{}_2hbox {O} thin film on a transparent substrate that showcases Rydberg excitons up to n = 8 which is readily suitable for photonic device fabrications. These findings mark a significant advancement towards the realization of scalable and on-chip integrable Rydberg quantum technologies.

Enhanced nitrobenzene sensing in metal anchored gamma-graphyne: predictions from density functional theory

Nitrobenzene (NB), being a toxic industrial effluent, its adsorption performance on pristine and metals (Al, Cu and Sc) anchored 2D graphyne (GY) monolayer was studied systematically via the first principles DFT simulations. The NB was found to be weakly adsorbed on the pristine monolayer with an energy of −0.46 eV due to the long-range van der Waals interactions. The NB was strongly adsorbed on the anchored metal site except for the case of Cu. The adsorption energy calculations suggest that the Al-anchored GY monolayer is excellent for the NB sensing because of the reasonable adsorption energy of −1.18 eV, charge transfer of 0.57 e and attainable recovery time of 2.4 s at 450 K. The work function sensitivity of the Al anchored system towards the NB molecule is 10% higher than the pristine system. Moreover, the ab-initio molecular dynamics simulations have predicted the room temperature structural steadiness of the Al-anchored GY monolayer. Overall, our research suggests that the Al-anchored GY monolayer is promising to adsorb the NB molecules effectively and can be potentially applied as an excellent NB biomolecule sensor.

How the Temperature and Composition Govern the Structure and Band Gap of Zr-Based Chalcogenide Perovskites: Insights from ML Accelerated AIMD.

The effects of temperature and composition on the structural and electronic properties of chalcogenide perovskite (CP) materials AZrX3 (A = Ba, Sr, Ca; X = S, Se) in the distorted perovskite (DP) phase are investigated using ab initio molecular dynamics (AIMD) accelerated by machine-learned force fields. Long-range van der Waals (vdW) interactions, incorporated into the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional using the DFT-D3 scheme, are found to be crucial for achieving correct predictions of structural parameters. Our calculations show that the distortion of the DP structure with respect to the parent cubic (C) phase, realized in the form of interoctahedral tilting, decreases with the increasing size of the A cations. The tendency for a gradual transformation of the DP-to-C phase with increasing temperature is shown to be strongly composition-dependent. The transformation temperature decreases with the size of cation A and increases with the size of anion X. Thus, within the range of the temperatures considered here (300-1200 K), a complete transformation is observed only for BaZrS3 (∼600 K) and BaZrSe3 (∼900 K). The computed band gap of CPs is shown to monotonically decrease with increasing temperature, and the magnitude of this decrease is found to be proportional to the extent of the thermally induced changes in the internal structure. Diverse factors affecting the magnitude of band gaps of CP materials are analyzed.

Insight into the role of pseudo-halides as multiple hydrogen bond acceptors in the formation of supramolecular 1D assembly of di and trinuclear zinc complexes

In this manuscript we report the synthesis of two new zinc(II) complexes, [(DMSO)2 ZnL1Zn(NCS)2] (1), and [{(N3)ZnL2}2Zn(DMSO)2] (2) that were characterized by elemental and spectral analyses {H2L1 is 2,2-dimethyl-1,3-propanediylbis(iminomethylene)bis(phenol), and H2L2 is 1,2-propanediylbis(iminomethylene)bis(4-chlorophenol)}. The structures have been confirmed by single crystal X-ray diffraction analysis. Both complexes form 1D supramoelcular assemblies where the pseudohalides act as multiple H-bond acceptors (CH•••S,N and NH•••S,N). These assemblies have been analyzed theoretically using DFT calculations, and the energy associated to each contact has been estimated using the quantum theory of atoms-in-molecules. The importance of long-range van der Waals interactions is emphasized. This manuscript, where two new complexes are synthesized and the H-bonding contacts individually estimated, is expected to attract the attention not only of synthetic inorganic chemists, but also theoreticians and chemists working in crystal engineering and supramolecular chemistry.

Complex ligand adsorption on 3D atomic surfaces of synthesized nanoparticles investigated by machine-learning accelerated ab initio calculation.

Nanoparticle surfaces are passivated by surface-bound ligands, and their adsorption on synthesized nanoparticles is complicated because of the intricate and low-symmetry surface structures. Thus, it is challenging to precisely investigate ligand adsorption on synthesized nanoparticles. Here, we applied machine-learning-accelerated ab initio calculation to experimentally resolved 3D atomic structures of Pt nanoparticles to analyze the complex adsorption behavior of polyvinylpyrrolidone (PVP) ligands on synthesized nanoparticles. Different angular configurations of large-sized ligands are thoroughly investigated to understand the adsorption behavior on various surface-exposed atoms with intrinsic low-symmetry. It is revealed that the ligand binding energy (Eads) of the large-sized ligand shows a weak positive relationship with the generalized coordination number . This is because the strong positive relationship of short-range direct bonding (Ebind) is attenuated by the negative relationship of long-range van der Waals interaction (EvdW). In addition, it is demonstrated that the PVP ligands prefer to adsorb where the long-range vdW interaction with the surrounding surface structure is maximized. Our results highlight the significant contribution of vdW interactions and the importance of the local geometry of surface atoms to the adsorption behavior of large-sized ligands on synthesized nanoparticle surfaces.

Study of physisorption of aromatic molecules on hydroxylated α-SiO2 (0 0 1) surface using dispersion-corrected density functional theory

In this work, the interactions are investigated in a series of aromatic molecules adsorbed on hydroxylated (001) surface of α-SiO2 using density functional theory with dispersion correction. It is observed that the van der Waals interactions are strongly dependent on the kind of aromatic molecules. For the molecules of heavy halogen, it shows the strong interaction compared to that of benzene molecule due to its large electron affinity of aromatic molecules. Oxygen-based aromatic molecules are very active and easily to from weak hydrogen bond with hydroxylated surface at tilted configurations. The interaction can be attributed mainly to the weak hydrogen bond and short-range van der Waals interaction. The magnitude of weak hydrogen bond is comparable with that of van der Waals dispersion interaction of benzene ring at flat configuration. For non-polar aromatic molecules, the flat configuration is more stable due to the strong van der Waals interaction of benzene ring. Newly SCAN-rVV10 functional offers precise description for capturing the medium and long-range van der Waals interaction in adsorbate–surface. This study offers theoretical guideline for the design and application of aromatic-based molecules in the fields of catalysis, tribology and electronic devices.

Ab Initio Study of High-Capacity Hydrogen Storage in Lithium-Shrouded Honeycomb Borophene Oxide Nanosheet

Here, we investigate the hydrogen storage performance of Li alkali metal-shrouded two-dimensional (2D) honeycomb borophene oxide (h-B3O) using the Tkatchenko–Scheffler method, an accurate and parameter-free method to determine the long-range van der Waals interactions. Each Li atom can strongly bind three H2 molecules to the substrate with an average adsorption energy of −0.22 eV/H2, and the theoretical weight density of the Li-shrouded h-B3O structure can reach 9.84 wt %. In particular, a maximum hydrogen storage capacity of 12.71 wt % is achievable by moderately increasing the external pressure. Lattice thermal conductivity calculations show efficient thermal transport and good adsorption/desorption behavior of H2 molecules. Furthermore, the study of possible defects in the material showed that the hydrogen storage performance of the Li-shrouded h-B3O nanosheet is insensitive to the presence of defects in the material, which has important implications for its experimental synthesis. Our findings indicate that Li-shrouded 2D h-B3O is a promising material for reversible H2 storage.

Controlled filamentation instability as a scalable fabrication approach to flexible metamaterials

Long and flexible arrays of nanowires find impactful applications in sensing, photonics, and energy harvesting. Conventional manufacturing relies largely on lithographic methods limited in wafer size, rigidity, and machine write time. Here, we report a scalable process to generate encapsulated flexible nanowire arrays with high aspect ratios and excellent tunable size and periodicity. Our strategy is to control nanowire self-assembly into 2D and 3D architectures via the filamentation of a textured thin film under anisotropic stretching. This is achieved by coupling soft lithography, glancing angle deposition, and thermal drawing to obtain well-ordered meters-long nanowires with diameters down to 50 nanometers. We demonstrate that the nanowire diameter and period of the array can be decoupled and manipulated independently. We propose a filamentation criterion and perform numerical simulations implementing destabilizing long-range Van der Waals interactions. Applied to high-index chalcogenide glasses, we show that this decoupling allows for tuning diffraction. Finally, harnessing Mie resonance, we demonstrate the possibility of manufacturing macroscopic meta-grating superstructures for nanophotonic applications.

Performance and interaction mechanism of a new highly efficient benzimidazole-based epoxy resin for corrosion inhibition of carbon steel in HCl: A study based on experimental and first-principles DFTB simulations

Thanks to their excellent properties, epoxy resins are the first choice for many engineering applications. In this regard, herein, a new epoxy resin, namely 1-(oxiran-2-ylmethyl-1H-benzo[d]imidazole (BIZ epoxy), was synthesized and characterized by nuclear magnetic resonance (1H, 13C NMR) and Fourier transform infrared-attenuated total reflection (FTIR-ATR)) techniques. The corrosion inhibition properties of prepared epoxy resin for carbon steel (CS) in 1.0 mol/L HCl were evaluated using electrochemical and scanning electron microscope (SEM) techniques. Furthermore, reactivity and interaction mechanisms between epoxy resin molecule and the iron surface were investigated using quantum chemical parameters (QCPs) and Density-Functional Tight-Binding (DFTB). Electrochemical studies by potentiodynamic polarization curves (PPC) and electrochemical impedance spectroscopy (EIS) showed that the BIZ epoxy acted as a barrier against the acid corrosion of CS with an inhibition efficiency of 93 % at 1 mmol/L. The adsorption of BIZ epoxy followed the Langmuir adsorption isotherm and was found to be a physicochemical process. The SEM analysis showed a significant difference in surface morphology of CS after inhibition due to the formation of a protective barrier. DFTB simulation of BIZ epoxy – Fe(110) surface revealed the formation of a chemical bond and several long-range van der Waals interactions. The projected density of states (PDOS) of isolated and adsorbed systems confirmed the physicochemical nature of interactions between inhibitor molecule and Fe(110) surface.

Accessing Thin Film Wetting Regimes during Polymer Growth by Initiated Chemical Vapor Deposition.

We investigate the growth of a fluorinated polymer via initiated chemical vapor deposition onto a suite of isotropic and mesogenic liquids with a range of refractive indices. The polymer morphology at fluid interfaces was found to deviate from conformal films predicted by the positive spreading coefficient, and the resulting morphology is attributed to long-range van der Waals interactions during the deposition process. Experiments systematically vary the deposition conditions and compare the liquid phase (isotropic or nematic) to evaluate the effect of kinetic factors and the liquid substrate phase on the interfacial polymer morphology and spatial organization.

Clustering, collision, and relaxation dynamics in pure and doped helium nanoclusters: Density- vs particle-based approaches.

The clustering, collision, and relaxation dynamics of pristine and doped helium nanodroplets is theoretically investigated in cases of pickup and clustering of heliophilic argon, collision of heliophobic cesium atoms, and coalescence of two droplets brought into contact by their mutual long-range van der Waals interaction. Three approaches are used and compared with each other. The He time-dependent density functional theory method considers the droplet as a continuous medium and accounts for its superfluid character. The ring-polymer molecular dynamics method uses a path-integral description of nuclear motion and incorporates zero-point delocalization while bosonic exchange effects are ignored. Finally, the zero-point averaged dynamics approach is a mixed quantum-classical method in which quantum delocalization is described by attaching a frozen wavefunction to each He atom, equivalent to classical dynamics with effective interaction potentials. All three methods predict that the growth of argon clusters is significantly hindered by the helium host droplet due to the impeding shell structure around the dopants and kinematic effects freezing the growing cluster in metastable configurations. The effects of superfluidity are qualitatively manifested by different collision dynamics of the heliophilic atom at high velocities, as well as quadrupole oscillations that are not seen with particle-based methods, for droplets experiencing a collision with cesium atoms or merging with each other.

Interfacial Selective Study on the Gelation Behavior of Aqueous Methylcellulose Solution via a Quartz Crystal Microbalance.

It is important to understand the interfacial structure and physical properties of a polymer material to improve its function. In this study, we used a quartz crystal microbalance (QCM) and neutron reflectivity (NR) measurements to evaluate the viscoelasticity and structure of an aqueous methylcellulose solution near the gold interface. The apparent shear modulus, which was calculated from the complex frequency, was used to assess gelation behavior. The apparent shear modulus determined via the QCM suggested high-frequency rheological properties that reflected the relaxation of skeletal stretching and rotational motion of polymer segments, as well as cooperative motion of the various functional groups. The gelation temperature was found to be lowered at the interface in comparison with that of the bulk. It is suggested that the QCM can evaluate the shear modulus accompanying the gelation near the interface. The interfacial segregation on the gold substrate caused by the surface free energy and long-range van der Waals interaction was observed from NR measurements.

Accurate Simulations of Lipid Monolayers Require a Water Model with Correct Surface Tension.

Lipid monolayers provide our lungs and eyes their functionality and serve as proxy systems in biomembrane research. Therefore, lipid monolayers have been studied intensively including using molecular dynamics simulations, which are able to probe their lateral structure and interactions with, e.g., pharmaceuticals or nanoparticles. However, such simulations have struggled in describing the forces at the air–water interface. Particularly, the surface tension of water and long-range van der Waals interactions have been considered critical, but their importance in monolayer simulations has been evaluated only separately. Here, we combine the recent C36/LJ-PME lipid force field that includes long-range van der Waals forces with water models that reproduce experimental surface tensions to elucidate the importance of these contributions in monolayer simulations. Our results suggest that a water model with correct surface tension is necessary to reproduce experimental surface pressure–area isotherms and monolayer phase behavior. The latter includes the liquid expanded and liquid condensed phases, their coexistence, and the opening of pores at the correct area per lipid upon expansion. Despite these improvements of the C36/LJ-PME with certain water models, the standard cutoff-based CHARMM36 lipid model with the 4-point OPC water model still provides the best agreement with experiments. Our results emphasize the importance of using high-quality water models in applications and parameter development in molecular dynamics simulations of biomolecules.

First-principles calculations of defects in metal halide perovskites: A performance comparison of density functionals

Metal halide perovskite semiconductors have outstanding optoelectronic properties. Although these perovskites are defect-tolerant electronically, defects hamper their long-term stability and cause degradation. Density functional theory (DFT) calculations are an important tool to unravel the microscopic structures of defects, but results suffer from the different approximations used in the DFT functionals. In the case of metal halide perovskites, qualitatively different results have been reported with different functionals, either predicting vacancy or interstitial point defects to be most dominant. Here, we conduct a comprehensive comparison of a wide range of functionals for calculating the equilibrium defect formation energies and concentrations of point defects in the archetype metal halide perovskite, ${\mathrm{MAPbI}}_{3}$. We find that it is essential to include long-range van der Waals interactions in the functional, and that it is vital to self-consistently optimize structure and volume of all compounds involved in the defect formation. For calculating equilibrium formation energies of point defects in ${\mathrm{MAPbI}}_{3}$ and similar metal halide perovskites, we argue that the exact values of the chemical potentials of the species involved, or of the intrinsic Fermi level, are not important. In contrast to the simple Schottky or Frenkel pictures, we find that the dominant defects are MA and I interstitials, and Pb vacancies.

Study of structural phase transition and elastic properties of ZnTe semiconducting compound under high pressure

The high-pressure structural phase transition and pressure induced elastic properties of cubic zinc-blende phase (B3) to rock-salt phase (B1) structure of Zinc Telluride (ZnTe) semiconducting compound were studied by using the effective inter-ionic potential method, which contains the long-range Coulomb and van der Waals (vdW) interactions and the short-range repulsive interaction of up to second-neighbor ions within the Hafemeister and Flygare approach. The structural phase transition from B3 to B1 structure is reflected using estimated values of phase transition pressure and volumetric abrupt changes in the pressure–volume phase diagram. The calculated results first predict the phase transformation of ZnTe from B3 to B1, which occurs at 19GPa and is consistent with the reported data. Later on, using the effective inter-ionic potential technique, we were able to predict the second order elastic characteristics of the ZnTe system.

Dipole-dipole-interaction–driven antiblockade of two Rydberg atoms

Resonant laser excitation of multiple Rydberg atoms are prohibited, leading to Rydberg blockade, when the long-range van der Waals interactions are stronger than the laser-atom coupling. Rydberg blockade can be violated, i.e., simultaneous excitation of more than one Rydberg atom, by off-resonant laser excitation, causing an excitation antiblockade. Rydberg antiblockade gives rise to strongly correlated many-body dynamics and spin-orbit coupling and also finds quantum computation applications. Instead of commonly used van der Waals interactions, we investigate antiblockade dynamics of two Rydberg atoms interacting via dipole-dipole exchange interactions. We study typical situations in current Rydberg atom experiments, where different types of dipole-dipole interactions can be achieved by varying Rydberg state couplings. An effective Hamiltonian governing underlying antiblockade dynamics is derived. We illustrate that geometric gates can be realized with the Rydberg antiblockade which is robust against the decay of Rydberg states. Our study may stimulate new experimental and theoretical exploration of quantum optics and strongly interacting many-body dynamics with Rydberg antiblockade driven by dipole-dipole interactions.