Van Der Waals Dispersion Interactions Research Articles

LibMBD: A general-purpose package for scalable quantum many-body dispersion calculations.

Many-body dispersion (MBD) is a powerful framework to treat van der Waals (vdW) dispersion interactions in density-functional theory and related atomistic modeling methods. Several independent implementations of MBD with varying degree of functionality exist across a number of electronic structure codes, which both limits the current users of those codes and complicates dissemination of new variants of MBD. Here, we develop and document libMBD, a library implementation of MBD that is functionally complete, efficient, easy to integrate with any electronic structure code, and already integrated in FHI-aims, DFTB+, VASP, Q-Chem, CASTEP, and Quantum ESPRESSO. libMBD is written in modern Fortran with bindings to C and Python, uses MPI/ScaLAPACK for parallelization, and implements MBD for both finite and periodic systems, with analytical gradients with respect to all input parameters. The computational cost has asymptotic cubic scaling with system size, and evaluation of gradients only changes the prefactor of the scaling law, with libMBD exhibiting strong scaling up to 256 processor cores. Other MBD properties beyond energy and gradients can be calculated with libMBD, such as the charge-density polarization, first-order Coulomb correction, the dielectric function, or the order-by-order expansion of the energy in the dipole interaction. Calculations on supramolecular complexes with MBD-corrected electronic structure methods and a meta-review of previous applications of MBD demonstrate the broad applicability of the libMBD package to treat vdW interactions.

High-Throughput Computational Screening of Two-Dimensional Covalent Organic Frameworks (2D COFs) for Capturing Radon in Moist Air.

Radon (Rn) and its decay products are the primary sources of natural ionizing radiation exposure for the public, posing significant health risks, including being a leading cause of lung cancer. Porous material-based adsorbents offer a feasible and efficient solution for controlling Rn concentrations in various scenes to achieve safe levels. However, due to competitive adsorption between Rn and water, finding candidates with a higher affinity and capacity for capturing Rn in humid air remains a significant challenge. Here, we conducted high-throughput computational screening of 8641 two-dimensional covalent organic frameworks (2D COFs) in moist air using grand canonical Monte Carlo simulations. We identified the top five candidates and revealed the structure-performance relationship. Our findings suggest that a well-defined cavity with an approximate spherical inner space, with a diameter matching that of Rn, is the structural basis for a proper Rn capturing site. This is because the excellent steric match between the cavity and Rn maximizes their van der Waals dispersion interactions. Additionally, the significant polarization electrostatic potential surface of the cavity can regulate the adsorption energy of water and ultimately impact Rn selectivity. Our study offers a potential route for Rn management using 2D COFs in moist air and provides a scientific basis for further experimentation.

Reimagining the Wave Function in Density Functional Theory: Exploring Strongly Correlated States in Pancake-Bonded Radical Dimers

Pancake bonding between π-conjugated radicals challenges conventional electronic structure approximations, due to the presence of both dispersion (van der Waals) interactions and "strong" electron correlation. Here we use a reimagined wave function-in-density functional theory (DFT) approach to model pancake bonds. Our generalized self-interaction correction extends DFT's reference system of noninteracting electrons, by introducing electron-electron interactions within an active space. We show that a small variation on our previous derivation recovers a DFT-corrected complete active space method proposed by Pijeau and Hohenstein. Comparison of the two approaches shows that the latter provides reasonable dissociation curves for single bonds and pancake bonds, including excited states inaccessible to conventional linear response time-dependent DFT. The results motivate broader adoption of wavefunction-in-DFT approaches for modeling pancake bonds.

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.

Tuning Interfacial Concentration Enhancement through Dispersion Interactions to Facilitate Heterogeneous Nucleation.

Classical molecular dynamics simulations were used to investigate how dispersion (van der Waals) interactions between non-polar, hydrophobic surfaces and aqueous glycine solutions affect the solution composition, molecular orientation, and dynamics at the interface. Simulations revealed that dispersion interactions lead to a major increase in the concentration of glycine at the interface in comparison with the bulk solution, resulting from a competition between solute and solvent molecules to be or not to be near the interface. This can then lead to kinetic and/or structural effects facilitating heterogeneous nucleation of glycine at non-polar surfaces, in agreement with recent observations for tridecane, graphene, and polytetrafluoroethylene. A novel parameterization process was developed to map a model surface with tunable dispersion interactions to heptane, tridecane, and graphite materials. The model surface was capable of reproducing the solution structure observed in fully atomistic simulations with excellent agreement and also provided good agreement for dynamic properties, at a significantly reduced computational cost. This approach can be used as an effective tool for screening materials for heterogeneous nucleation enhancement or suppression, based on non-specific dispersion interactions based on bulk material molecular properties, rather than interfacial functional groups, templating or confinement effects.

The effect of hydrostatic compression on the crystal structure of glycinium phosphite

The crystal structure of glycinium phosphite (GPI) was studied in the pressure range from ambient to 6.5 GPa at 293 K using single-crystal X-ray diffraction. The changes in the unit-cell volume and parameters were continuous and anisotropic. The major compression was observed normal to the direction of the spontaneous polarization that occurs in this structure during a ferroelectric phase transition on cooling, whereas the structural compression along the b axis coinciding with the 21 axis was almost zero. The effect of pressure on the hydrogen bonds linking the H2PO3 tetrahedra into zigzag chains along the c axis was different from that on the hydrogen bonds connecting the glycinium cations with the H2PO3 tetrahedra in the (b × c) plane. The discontinuous changes in the geometries of selected hydrogen bonds at about 1.21 GPa may be evidence of a phase transition, e.g. into an ordered ferroelectric phase (with ordered positions of protons). The anisotropy of compression of GPI in the ferroelectric state (at 0 K) was studied using DFT calculations taking into account dispersive van der Waals interactions. The calculations predicted negative linear compressibility along the b axis.

Tracing the origin of heterogeneities in the local structure and very sluggish dynamics of [Cho][Gly] ionic liquid confined between rutile and graphite slit nanopores: A MD study

Atomistic-level understanding of the interfacial behavior of ionic liquids (ILs) confined in slit-like nanopores is of both fundamental and practical interest. Molecular dynamics (MD) is an efficient and robust approach to characterize the properties of confined systems in contrast with some limitations in direct experimental measurements at low-dimensions. In this research, MD simulations are used to study the biocompatible IL cholinium glycinate, [Cho][Gly], confined between two parallel plates of rutile or graphite, with the separation distance of 24 Å along the z-direction. As expected, both the microscopic local structure and dynamical behavior of the confined IL are very heterogeneous and depend effectively on the position of the ions to the pore walls. The ion z-density profile is used for segmentation of the inter-wall space into a central region and two outer layers. The behavior of ions in the central region is very similar to the bulk IL, while the behavior of the arranged ionic layers adjacent to the pore walls shows the clear deviation from the bulk IL due to confinement. In general, the confined IL shows a "solid-like" dynamics at T = 353K, especially in the outer layers near the walls as well as in the z-direction. The presence of the "IL-rutile wall" electrostatic interaction and hydrogen bonding (H-bonding) causes a significant difference in the local structure and very sluggish dynamics of the IL adjacent to the rutile walls vs the graphite walls. Simulation reveals a significant decrease in the average number of key cation-anion H-bonds at the outer layers relative to the central regions of both confined systems. The recognized [Cho]+⋯[Gly]-⋯[Cho]+ bridge structure at the central region is lost in the vicinity of the rutile walls due to inaccessibility of the hydroxyl hydrogen atom, which forms a stable H-bond with the rutile oxygen site. However, another unprecedented [Gly]- bridge is confirmed and preserved near the graphite walls, and [Cho]+ cations prefer to stay parallel to the wall surface to form the van der Waals dispersion interactions with the uncharged graphite walls.

Industrial byproducts for the soil stabilization of trace elements and per- and polyfluorinated alkyl substances (PFASs)

The present work was the first exploration of the use of industrial byproducts from iron and titanium processing as sorbents for the stabilization of soil contamination. The main aim was to test slag waste and iron-rich charred fossil coal (“Fe-char”), as sorbents for per- and polyfluorinated alkyl substances (PFASs), as well as lead (Pb) and antimony (Sb), in four soils from a firefighting training area (PFASs) and a shooting range (Pb and Sb).Adding slag (10–20%) to shooting range soils decreased the leaching of Pb and Sb up to 50–90%. Fe-char amendment to these soils resulted in a moderate reduction in Sb leaching (20–70%) and a slightly stronger effect on Pb (40–50%). The sorption is most likely explained by the presence of Fe oxyhydroxides. These are present in the highest concentrations in the slag, probably resulting in more effective metal binding to the slag than to the Fe-char.Fe-char but not slag proved to be a strong sorbent for PFASs (reducing PFAS leaching from the soil by up to 99.7%) in soil containing low total organic carbon (TOC; 1.2%) but not in high-TOC soil (34%). The sorption coefficient KD for Fe-char was high, in the range of 104.3 to 106.5 L/kg at 1 ng/L in the low-TOC soil. The KD value increased with increasing perfluorocarbon chain length, exceeding PFAS sorption to biochar in the low ng/L concentration range. This result indicates that the mechanism behind the strong PFAS sorption to Fe-char was mainly van der Waals dispersive interactions between the hydrophobic PFAS-chain and the aromatic π-electron systems on nanopore walls within the Fe-char matrix.Overall, this study indicates that industrial byproducts can provide sustainable and cost-effective materials for soil remediation. However, the sorbent needs to be tailored to the type of soil and type of contamination.

Mechanisms of the Effects of Short-Term Inhalations of Xe and O2 Gas Mixture in the Rehabilitation of Post-COVID Ventilation Failure

The article presents a theoretical rationale and a clinical case of relief of post-COVID ventilation failure by inhalation of Xe and O2 gas mixture. Pneumonitis of coronavirus etiology transforms saturated phospholipids of surfactant into a solid-ordered phase, which disrupts surface tension, alveolar pneumatization, and alveolar-capillary gas exchange. Using molecular modeling (B3LYP/lanl2dz; GAUSSIAN09), we demonstrated that Xe atom due to the van der Waals dispersion interaction increases the distance between the phospholipid acyl chains providing a phase transition from the solid-ordered to liquid phase and restored the surface-active monolayer surfactant film. A clinical case confirmed that short-term inhalations of the Xe and O2 gas mixture relieved manifestations of ventilation insufficiency and increased SpO2 and pneumatization of the terminal parts of the lungs.

Electron beam analysis induces Cl vacancy defects in a NaCl thin film

This work reports on the electron-induced modification of NaCl thin film grown on Ag(110). We show using low energy electron diffraction that electron beam bombardment leads to desorption and formation of Cl vacancy defects on NaCl surface. The topographic structure of these defects is studied using scanning tunneling microscopy (STM) showing the Cl defects as depressions on the NaCl surface. Most of the observed defects are mono-atomic vacancies and are located on flat NaCl terraces. Auger electron spectroscopy confirms the effect of electron exposure on NaCl thin films showing Cl atoms desorption from the surface. Using density functional theory taken into account the van der Waals dispersion interactions, we confirm the observed experimental STM measurements with STM simulation. Furthermore, comparing the adsorption of defect free NaCl and defective NaCl monolayer on Ag(110) surfaces, we found an increase of the adhesion energy and the charge transfer between the NaCl film and the substrate due to the Cl vacancy. In details, the adhesion energy increases between the NaCl film and the metallic Ag substrate from 30.4 meV Å−2 for the NaCl film without Cl vacancy and from 39.5 meV Å−2 for NaCl film with a single Cl vacancy. The charge transfer from the NaCl film to the Ag substrate is enhanced when the vacancy is created, from 0.63e− to 1.25e−.

Effective Hamiltonians in Nonrelativistic Quantum Electrodynamics

In this paper, we consider some second-order effective Hamiltonians describing the interaction of the quantum electromagnetic field with atoms or molecules in the nonrelativistic limit. Our procedure is valid only for off-energy-shell processes, specifically virtual processes such as those relevant for ground-state energy shifts and dispersion van der Waals and Casimir-Polder interactions, while on-energy-shell processes are excluded. These effective Hamiltonians allow for a considerable simplification of the calculation of radiative energy shifts, dispersion, and Casimir-Polder interactions, including in the presence of boundary conditions. They can also provide clear physical insights into the processes involved. We clarify that the form of the effective Hamiltonian depends on the field states considered, and consequently different expressions can be obtained, each of them with a well-defined range of validity and possible applications. We also apply our results to some specific cases, mainly the Lamb shift, the Casimir-Polder atom-surface interaction, and the dispersion interactions between atoms, molecules, or, in general, polarizable bodies.

Stereoelectronic effects in stabilizing protein-N-glycan interactions revealed by experiment and machine learning.

The energetics of protein-carbohydrate interactions, central to many life processes, cannot yet be predictably manipulated. This is mostly due to an incomplete quantitative understanding of the enthalpic and entropic basis of these interactions in aqueous solution. Here, we show that stereoelectronic effects contribute significantly to stabilizing protein–N-glycan interactions in the context of a cooperatively folding protein. Double-mutant cycle analyses of the folding data from 52 electronically-varied N-glycoproteins demonstrate an enthalpy-entropy compensation depending on the electronics of the interacting side-chains. Linear and non-linear models obtained using quantum mechanical calculations and machine learning explain up to 79 and 97 % of the experimental interaction energy variability as inferred from the R2 value of the respective models. Notably, protein-carbohydrate interaction energies strongly correlate with the molecular orbital energy gaps of the interacting substructures. This suggests that stereoelectronic effects must be given a greater weight than previously thought for accurately modelling the short-range dispersive van der Waals interactions between the N-glycan and the protein.

DFT study on the sensitivity of silver-graphene quantum dots for vital and harmful analytes

DFT study is performed to evaluate the sensitivity and selectivity of silver, coronene, and silver-coronene composites for the detection of gaseous analytes including ethanol, ammonia, hydrogen sulfide, and oxygen molecules. Results of interaction energies reveal that O2@Ag6-coronene (−61.06 kcal mol−1) is the most stable while NH3@coronene is the least stable (−4.00 kcal mol−1) complex. The order of Eint and % reduction in H-Lgaps are the same for analyte@Ag6 complexes i.e. O2@Ag6 > NH3@Ag6 > C2H5OH@Ag6 > H2S@Ag6. Oxygen molecule strongly interacts with silver cluster due to strong Ag⋯O electrostatic interactions. Charge transfer interactions are explored through natural bond orbital (NBO) and charge decomposition (CDA) analyses. The frontier molecular orbital (FMO) analysis reveals a significant reduction in H-Lgap in the complexes of analytes with silver-coronene composites. UV–Visible results show that the absorption maximum is shifted towards a longer wavelength (bathochromic or red shift) in most of the complexes. Non-covalent interaction (NCI) study reveals that, besides strong electrostatic interactions, weak van der Waals dispersion interactions are present in silver-coronene complexes of analytes. The generation of new energy states in occupied and virtual orbitals closer to the Fermi level in the density of state (DOS) spectra affirm the sensitivity of silver-coronene composites towards analytes. The current findings suggest that silver-coronene composites are highly selective for the sensing of oxygen molecule. The outcome of the recent study will help to design the silver-graphene sensors for selective and accurate detection of analytes.

Сжимаемость и электронные свойства цианидов металлов

The compressibility and electronic properties of metal cyanides are investigated within the density functional theory taking into account the dispersion van der Waals interaction. It was shown that gold cyanide has a low linear compressibility (less than 0.1% at a pressure of 1 GPa) and a high linear modulus (~ 1200 GPa) along the -Au-CN-Au-CN- chains. Silver cyanide exhibits negative linear compressibility, which correlates with the compressibility of Ag-N coordination bonds. For sodium cyanide, the linear compressibility along the C - N covalent bonds is greater than for gold and silver cyanides, while the elastic anisotropy is less. Unlike sodium cyanide, for gold and silver cyanides, cation-anionic bonds (Au-N, Au-C and Ag-N, Ag-C) are partially covalent in nature, and the upper valence states correspond mainly to the states of cations. The band gap of gold cyanide is smaller than that of silver and sodium cyanides. The band gap widths of gold and silver cyanides significantly decrease with increasing pressure, which indicates the possibility of metallization at sufficiently high pressures.

Влияние эффекта испарения на устойчивость тонкого слоя жидкости в задаче Ландау–Левича

The stability of the liquid layer in the Landau–Levich problem is theoretically investigated in the presence of the evaporation effect from the free surface. The free energy of a thin layer of an incompressible fluid is the sum of the dispersion (van der Waals) interaction and the specific electrical interaction caused by the presence of double electric layers at both interphase boundaries. The stability of such a system with respect to perturbations is studied in the framework of the long – wave approximation in the system of Navier-Stokes equations. A stability map is provided for different values of the evaporation parameter. It is established that the stability of the system increases with an increase in the dimensionless number of evaporation.

Measurements and analysis of xanthate chain length effect on bubble attachment to galena surfaces

Although available flotation experiments show that sulphide flotation recovery increases with increasing xanthate chain length, quantitative analysis to reveal the underlying mechanisms is missing. Herein, we investigate the chain length effect by using a recently developed attachment apparatus and an advanced theory to determine and validate the attachment time of air bubbles to galena surfaces in solutions of ethyl, propyl, butyl and amyl xanthate collectors. Specifically, the attachment time was accurately determined from either transient force curves or transient film thickness of the bubble-surface attachment. The theory was based on the film drainage theory and colloidal forces, which include the advanced multilayer dispersion (van der Waals) interactions and the electrical double-layer interaction. The multilayer dispersion theory has allowed us to describe the effect of galena hydrophobicity induced by the xanthate chain length in terms of interfacial gas enrichment (IGE) on the bubble-surface attachment. The experimental results show that the attachment time is greatly affected by both the hydrophobicity and the bubble size, and agree with the theoretical results. Critically, it was possible to accurately quantify the attachment time of the hydrophobised galena surfaces to bubbles using the measured transient force curves and the advanced multilayer dispersion theory incorporating the IGE layer. Finally, this study made it possible to explain the effect of the hydrophobicity and bubble size on attachment time and provides the principle for the attachment mechanism of hydrophobic minerals to air bubbles.

DFT Study of Si/Al Ratio and Confinement Effects on the Energetics and Vibrational Properties of some Aza-Aromatic Molecules Adsorbed on H-ZSM-5 Zeolite

The Si/Al ratio and confinement effects of zeolite framework on energetics and vibrational frequencies of pyridine and 4,4′-bipyridine adsorbed on Brønsted acid sites in the straight channel of H-ZSM-5 are investigated by DFT calculations at the B3LYP and M06-2X+D3 levels. The straight channel of H-ZSM-5 is simulated by a cluster of 32 tetrahedral centers covering the intersection between straight and zigzag channels. Pyridine and 4,4′-bipyridine adsorption at two different sites in the intersection (open region) and/or in the narrow region situated between two intersections (closed region) is studied. For two Si/Al ratios (31, 15), the ion pair complexes formed by proton transfer upon pyridine and 4,4′-bipyridine adsorption in the open region and for the first time in the closed region are characterized. Our results indicate: (i) the stability for all adsorption complexes is essentially governed by the dispersive van der Waals interactions and the open region is energetically more favorable than the closed region owing to the predominance of the dispersive interactions over the steric constraints exerted by the confinement effects; (ii) as the Al centers are sufficiently spaced apart, Si/Al ratio does not influence pyridine adsorption energy, but significantly affects the adsorption energies and the relative stability of 4,4′-bipyridine complexes; (iii) neither Si/Al ratio nor confinement significantly influence pyridine and 4,4′-bipyridine vibrational frequencies within their complexes.

Effects of van der Waals Dispersion Interactions in Density Functional Studies of Adsorption, Catalysis, and Tribology on Metals

We review the effect of van der Waals (vdW) dispersion interactions on the determination of adsorption energy, vibration frequency, catalytic activity, and tribological property of weak physisorpti...

An open quantum system theory for polarizable continuum models.

The problem of a solute described by Quantum Chemistry within a solvent represented as a polarizable continuum model (PCM) is here reformulated in terms of the open quantum systems (OQS) theory. Using its stochastic Schrödinger equation formulation, we are able to provide a more comprehensive picture of the electronic energies and the coupling between solute and solvent electronic dynamics. In particular, the OQS-PCM proves to be a unifying theoretical framework naturally including polarization and dispersion interactions, the effect of solvent fluctuations, and the non-Markovian solvent response. As such, the OQS-PCM describes the interplay between the solute and the solvent typical electronic dynamical times and yields both the standard PCM and the so-called Born-Oppenheimer solvation regime, where the solvent electronic response is considered faster than any electronic dynamics taking place in the solute. In analyzing the OQS-PCM, we obtained an expression for the solute-solvent dispersion (van der Waals) interactions, which is very transparent in terms of a physical interpretation based on fluctuations and response functions. Finally, we present various numerical tests that support the theoretical findings.

Medium-assisted van der Waals dispersion interactions involving chiral molecules

The van der Waals dispersion interaction between two chiral molecules in the presence of arbitrary magnetoelectric media is derived using perturbation theory. To be general, the molecular polarisabilities are assumed to be of electric, paramagnetic and diamagnetic natures, and the material environment is considered to possess a chiral electromagnetic response. The derived expressions of electric dipole polarisable–chiral, magnetic dipole susceptible–chiral, and diamagnetic susceptible–chiral, and chiral–chiral interaction potentials when added to the previously obtained contributions in the literature, form a complete set of dispersion interaction formulas. We present them in a unified form making use of electric–magnetic duality. As an application, the case of two anisotropic molecules embedded in a bulk magnetoelectric medium is considered, where we derive the retarded and non-retarded limits with respect to intermolecular distance.