Dispersion-corrected Density Functional Theory Calculations Research Articles

Slow Phase Transition-Induced Scan Rate Dependence of Spin Crossover in a Two-Dimensional Supramolecular Fe(III) Complex

Slow Phase Transition-Induced Scan Rate Dependence of Spin Crossover in a Two-Dimensional Supramolecular Fe(III) Complex

Zn Metal–Organic Framework with High Stability and Sorption Selectivity for CO2

By the employment of 5-amino-1H-tetrazole and pyromellitic acid ligands to assemble with Zn2+ ions, a three-dimensional3,4-connect fry network {[Zn2(HATZ)(ATZ)2(PMA)0.5]·(H2O)5}n (GUPT-1, HATZ = 5-amino-1H-tetrazole, H4PMA = pyromellitic acid) was isolated in the hydrothermal reaction, which features high stability and exhibits high adsorption selectivity of CO2/N2 (118) under ambient conditions and 1 bar. Moreover, grand canonical Monte Carlo (GCMC) simulation and the dispersion-corrected density functional theory (DFT-D) calculations reveal two types of binding sites: first, the electrostatic interactions between CO2 molecules and −NH2 groups exposed inside the channels and, second, the C···O interactions between the C atoms in the CO2 molecules and O atoms in the pyromellitic acid ligands. Furthermore, the static binding energy of CO2 molecules on GUPT-1 calculated by the DFT-D-simulated results was 38.49 kJ·mol–1, which corresponded to the experimental adsorption enthalpy (Qst) calculated to be 37.01 kJ·mol–1.

First-principles DFT insights into the mechanisms of CO2 reduction to CO on Fe (100)-Ni bimetals

Iron and nickel are known active sites in the enzyme carbon monoxide dehydrogenases which catalyzes CO2 to CO reversibly. The presence of nickel impurities in the earth abundant iron surface could provide a more efficient catalyst for CO2 degradation into CO, which is a feedstock for hydrocarbon fuel production. In the present study, we have employed spin-polarized dispersion-corrected density functional theory calculations within the generalized gradient approximation to elucidate the active sites on Fe (100)-Ni bimetals. We sort to ascertain the mechanism of CO2 dissociation to carbon monoxide on Ni deposited and alloyed surfaces at 0.25, 0.50 and 1 monolayer (ML) impurity concentrations. CO2 and (CO + O) bind exothermically i.e., − 0.87 eV and − 1.51 eV respectively to the bare Fe (100) surface with a decomposition barrier of 0.53 eV. The presence of nickel generally lowers the amount of charge transferred to CO2 moiety. Generally, the binding strengths of CO2 were reduced on the modified surfaces and the extent of its activation was lowered. The barriers for CO2 dissociation increased mainly upon introduction of Ni impurities which is undesired. However, the 0.5 ML deposited (FeNi0.5(A)) surface is promising for CO2 decomposition, providing a lower energy barrier (of 0.32 eV) than the pristine Fe (100) surface. This active 1-dimensional defective FeNi0.5(A) surface provides a stepped surface and Ni–Ni bridge binding site for CO2 on Fe (100). Ni–Ni bridge site on Fe (100) is more effective for both CO2 binding or sequestration and dissociation compared to the stepped surface providing the Fe–Ni bridge binding site.

Trilayer Metal-Organic Frameworks as Multifunctional Electrocatalysts for Energy Conversion and Storage Applications.

The need for enhanced energy storage and improved catalysts has led researchers to explore advanced functional materials for sustainable energy production and storage. Herein, we demonstrate a reductive electrosynthesis approach to prepare a layer-by-layer (LbL) assembled trimetallic Fe-Co-Ni metal-organic framework (MOF) in which the metal cations within each layer or at the interface of the two layers are linked to one another by bridging 2-amino-1,4-benzenedicarboxylic acid linkers. Tailoring catalytically active sites in an LbL fashion affords a highly porous material that exhibits excellent trifunctional electrocatalytic activities toward the hydrogen evolution reaction (ηj=10 = 116 mV), oxygen evolution reaction (ηj=10 = 254 mV), as well as oxygen reduction reaction (half-wave potential = 0.75 V vs reference hydrogen electrode) in alkaline solutions. The dispersion-corrected density functional theory calculations suggest that the prominent catalytic activity of the LbL MOF toward the HER, OER, and ORR is due to the initial negative adsorption energy of water on the metal nodes and the elongated O-H bond length of the H2O molecule. The Fe-Co-Ni MOF-based Zn-air battery exhibits a remarkable energy storage performance and excellent cycling stability of over 700 cycles that outperform the commercial noble metal benchmarks. When assembled in an asymmetric device configuration, the activated carbon||Fe-Co-Ni MOF supercapacitor provides a superb specific energy and a power of up to 56.2 W h kg-1 and 42.2 kW kg-1, respectively. This work offers not only a novel approach to prepare an LbL assembled multimetallic MOF but also provides a benchmark for a multifunctional electrocatalyst for water splitting and Zn-air batteries.

Pressure-induced phase transitions and mechanical properties of insensitive high explosive 1,1-diamino-2,2-dinitroethylene

Abstract The structural and mechanical properties of an insensitive high-explosive 1,1-diamino-2,2-dinitroethylene (FOX-7) polymorphs were studied using dispersion-corrected density functional theory calculations. The predicted lattice parameters of FOX-7 polymorphs agree well with the available single-crystal X-ray diffraction data. From our elastic modulus calculations, we found that the ε phase has the highest shear modulus G, Young’s modulus E, longitudinal speed C L, and shear speed C S, respectively. Moreover, both α and α′ phase are brittle, ε phase is ductile nature. The results of Hirshfeld surfaces and fingerprint plots indicate that the α and α′ phase possess similar molecular packing modes. Meanwhile, the ε phase is found to have the strongest π…π interactions because of the nearly planer molecules formed a planar layer in the crystal. The pressure effects on the α and α′ phase presented an obvious anisotropy, a pressure-induced phase transition from phase α′ (P21/n) to ε phase (P1) was studied. And we also analyze the influence of pressure on the electronic structure.

Structure and properties of dislocations and the twin boundary on (101) in β-cyclotetramethylene tetranitramine

ABSTRACT Dispersion-corrected density functional theory calculations of the generalised stacking fault energy surface of the (101) plane in monoclinic β-cyclotetramethylene tetranitramine (β-HMX) indicate that a stacking fault with an energy of approximately 130 mJ/m at the translation vector is metastable. Using the energy of the metastable stacking fault and anisotropic linear elasticity theory, we have evaluated whether dislocations with total Burgers vectors , and will split into partial dislocations on . Our results suggest that it is not favourable for the screw dislocation to split into partials but that the edge dislocation will split into partials separated by a narrow, 19.8 Å, stacking fault. Both screw and edge dislocations are predicted to split into two partials with splitting distances of about 28.7 and 43.4 Å, respectively. The screw and edge dislocation are also predicted to split into partials, with equilibrium distances of 16.3 and 43.2 Å, respectively. These results are consistent with recent analyses of Knoop indentation experiments in which the slip system is inactive whereas dislocations are glissile. Since twinning is an important deformation mechanism in β-HMX, dispersion-corrected density functional theory calculations have also been used to compute the energy of the twin boundary, for which we report a value of 163 mJ/m.

Coating all-boron B38 fullerene with Ca and Al atoms for enhancing CO2 capture: a DFT study

It is widely recognised that capturing and storing CO2 on porous materials is an efficient approach for lowering the concentration of this greenhouse gas in the atmosphere. The current work investigates the ability of Ca and Al decorated all-boron B38 fullerene to capture and store CO2 using dispersion-corrected density functional theory calculations. The results showed that Ca and Al atoms can both firmly attach to the boron atoms in the hexagon cavity of B38. This eliminates the clustering issue and may ensure the stability of the decorated B38 fullerenes. According to the findings, the B38 fullerene decorated with four Ca or Al atoms may retain up to 16 CO2 molecules, corresponding to a maximum gravimetric density of about 55 wt%. The adsorption energy per CO2 in the Ca and Al decorated systems is about −0.70 eV, which is within the range proposed for effective CO2 storage (−0.40 to −0.80 eV). As a result, Ca and Al decorated B38 fullerenes are efficient and promising materials for high-capacity CO2 storage.

Understanding delivery and adsorption of Flutamide drug with ZnONS based on: Dispersion-corrected DFT calculations and MD simulations

The unique features of zinc oxide nanosheet (ZnONS) as an appropriate platform for Flutamide molecule was considered by means of density functional theory (DFT) framework with van der Waals (vdW) approximation via Perdew–Burke–Ernzerhof variant of the generalized gradient approximation (PBE-GGA) method along with double zeta polarization (DZP) basis set. The most stable model of interaction between Flutamide molecule and ZnONS is specified and adsorption energies (Eads) are assessed. In energetically favorable configuration, O atoms of –NO2 group of Flutamide interacts with a Zn atom of the ZnONS at 2.11 Å with Eads of −20.616 kcal mol−1. We have scrutinized charge analysis between species involved through famous Mulliken, Hirshfeld and Voronoi approaches. Furthermore, we have examined the density of states (DOS) and the projected density of states (PDOS) for the energetically favorable model to explore the interaction of the drug molecule with the ZnONS. Besides, quantum molecular descriptors (QMD) are also analyzed upon interaction of drug molecule on ZnONS. To deeper knowledge the details of the interaction between the Flutamide and the ZnONS, Quantum Theory of Atoms in Molecules (QTAIM) calculations are implemented. The values of ▽2ρ(BCP) and H(BCP) for (Flutamide)O⋯Zn(ZnONS) at the most stable configuration are positive and G/|V| is greater than 1, it denotes the non-covalent interaction between Flutamide with ZnONS. The DFT calculation based on molecular dynamics (MD) approach are utilized to acquire a better understand into the nature of the Flutamide drug and ZnONS interactions. The MD outcomes demonstrate that when the Flutamide molecule takes longer time to link with ZnONS, the Flutamide/ZnONS complex becomes stable. Moreover, after Flutamide molecule adsorption phenomenon the electrical conductivity generates an electrical signal. The outcomes affirmed the potential of a ZnONS as a drug delivery system (DDS) for drug molecule to remedy cancer and may be an appropriate sensor for the Flutamide drug detection.

Expanding the Supramolecular Toolkit: Computed Molecular and Crystal Properties for Supporting the Crystal Engineering of Higher-Order Molecular Ionic Cocrystals

Over the past 2 decades, significant progress has been made in developing a robust supramolecular toolkit for the crystal engineering of simple binary cocrystals. By contrast, crystal engineering of higher-order molecular ionic cocrystals (ICCs) is not well established. Here, we report the results of the most extensive survey of the molecular and crystal properties of ICCs reported to date and use the resulting data to propose a set of guiding principles to aid the crystallization of molecular ICCs sustained by charge-assisted hydrogen bonding interactions. Using a data set comprising a total of 94 ICC crystal structures, this work reveals that molecular ICCs are favored within a narrow range of the property landscape. Specifically, most of the ICCs in the data set are crystallized using molecules with significantly different polar surface areas. The data also highlight the importance of choosing molecules with a similar number of conformational degrees of freedom when targeting higher-order cocrystals. Molecular ICCs comprising conjugate acid–base fragments are more likely to be observed in crystallization screens when the difference in the ionization constants of the acid–base pair lie within the “gray” zone of the salt–cocrystal continuum. This work also reveals the hierarchy in the supramolecular heterosynthons of molecular ICCs. Finally, periodic dispersion-corrected density functional theory calculations on a limited subset of crystal structures reveals that most of the ICCs surveyed are driven to form on the basis of favorable energetics as indicated by a mean stabilization energy of −5 kJ mol–1.

Nutraceuticals in Bulk and Dosage Forms: Analysis by 35Cl and 14N Solid-State NMR and DFT Calculations.

This study uses 35Cl and 14N solid-state NMR (SSNMR) spectroscopy and dispersion-corrected plane-wave density functional theory (DFT) calculations for the structural characterization of chloride salts of nutraceuticals in their bulk and dosage forms. For eight nutraceuticals, we measure the 35Cl EFG tensor parameters of the chloride ions and use plane-wave DFT calculations to elucidate relationships between NMR parameters and molecular-level structure, which provide rapid NMR crystallographic assessments of structural features. We employ both 35Cl direct excitation and 1H→35Cl cross-polarization methods to characterize a dosage form containing α-d-glucosamine HCl, observe possible impurity and/or adulterant phases, and quantify the weight percent of the active ingredient. To complement this, we also investigate 14N SSNMR spectroscopy and DFT calculations to characterize nitrogen atoms in the nutraceuticals. This includes a discussion of targeted acquisition experimental protocols (i.e., acquiring a select region of the overall pattern that features key discontinuities) that allow ultrawideline spectra to be acquired rapidly, even for unreceptive samples (i.e., those with long values of T1(14N), short values of T2eff(14N), or very broad patterns). It is hoped that these experimental and computational protocols will be useful for the characterization of various solid forms of nutraceuticals (i.e., salts, polymorphs, hydrates, solvates, cocrystals, amorphous solid dispersions, etc.), help detect impurity and counterfeit solid phases in dosage forms, and serve as a foundation for future NMR crystallographic studies of nutraceutical solid forms, including studies using ab initio crystal structure prediction algorithms.

Binding group of oligonucleotides on TiO2 surfaces: Phosphate anions or nucleobases?

Although the immobilization of oligonucleotides (nucleic acid) on mineral surfaces is at the basis of different biotechnological applications, an atomistic understanding of the interaction of the nucleic acid components with the titanium dioxide surfaces has not yet been achieved. Here, the adsorption of the phosphate anion, of the four DNA bases (adenine, guanine, thymine, and cytosine) and of some entire nucleotides and dinucleotides on the TiO2 anatase (101) surface is studied through dispersion-corrected hybrid density functional theory (DFT) calculations. Several adsorption configurations are identified for the separated entities (phosphate anion or base) and then considered when studying the adsorption of the entire nucleotides. The analysis shows that both the phosphate anion and each base may anchor the nucleotides to the surface in a collaborative and synergistic adsorption mode. The tendency is that the nucleotides containing the guanine base present the strongest adsorption while those made up with the thymine base have the lowest adsorption energies. Nucleotides based on adenine and cytosine have a similar intermediate behavior. Finally, we investigated the adsorption of competing water molecules to understand whether in the presence of the aqueous solvent, the nucleotides would remain bonded to the surface or desorb.

Registry-Dependent Potential for Interfaces of Gold with Graphitic Systems.

We present a semi-anisotropic interfacial potential (SAIP) designed to classically describe the interaction between gold and two-dimensional (2D) carbon allotropes such as graphene, fullerenes, or hydrocarbon molecules. The potential is able to accurately reproduce dispersion-corrected density functional theory (DFT+D3) calculations performed over selected configurations: a flat graphene sheet, a benzene molecule, and a C60 fullerene, physisorbed on the Au(111) surface. The effects of bending and hydrogen passivation on the potential terms are discussed. The presented SAIP provides a noticeable improvement in the state-of-the-art description of Au–C interfaces. Furthermore, its functional form is suitable to describe the interfacial interaction between other 2D and bulk materials.

Graphene-induced planarization of cyclooctatetraene derivatives.

Stable equilibrium compounds containing a planar antiaromatic cyclooctatetraene (COT) ring are promising candidates for organic electronic devices such as organic semiconductor transistors. The planarization of COT by incorporation into rigid planar π-systems, as well as by oxidation or reduction has attracted considerable attention in recent years. Using dispersion-corrected density functional theory calculations, we explore an alternative approach of planarizing COT derivatives by adsorption onto graphene. We show that strong π-π stacking interactions between graphene and COT derivatives induce a planar structure with an antiaromatic central COT ring. In addition to being reversible, this strategy provides a novel approach for planarizing COT without the need for incorporation into a rigid structure, atomic substitution, oxidation, or reduction.

Quantifying the influence of dispersion interactions on the elastic properties of crystalline cellulose

Dispersion and electrostatic interactions both contribute significantly to the tight assembly of macromolecular chains within crystalline polysaccharides. Using dispersion-corrected density functional theory (DFT) calculation, we estimated the elastic tensor of the four crystalline cellulose allomorphs whose crystal structures that are hitherto available, namely, cellulose Iα, Iβ, II, IIII. Comparison between calculations with and without dispersion correction allows quantification of the exact contribution of dispersion to stiffness at molecular level.

Metalloid Chalcogen–pnictogen σ-hole bonding competition in stibanyl telluranes

In this manuscript a curious behavior observed in the solid state of several X-ray structures retrieved from the Cambridge structural database (CSD) is described and analyzed. These structures have in common the presence of a metalloid–metalloid pnictogen (Pn)–chalcogen (Ch) covalent bond (i.e., Sb–Te bond) in the structure. The Sb–Te bond presents different σ-holes at both ends of the bond in terms of size and intensity. These compounds have a tendency to form short intermolecular Sb•••Te interactions in the solid state. The aim of this work is to investigate, by using dispersion-corrected density functional theory (DFT-D3) calculations, whether the Sb•••Te contacts observed in the solid state correspond to PnB (Sb is the Lewis acid) or ChB (Te is the Lewis acid). Moreover, using two model stibanyl telluranes, the interaction energies with a series of Lewis bases and anions using both ends of the Sb–Te covalent bond have been computed to investigate which side (PnB or ChB donor) is able to establish stronger interactions with common electron rich atoms. Finally, several computational tools such as the quantum theory of atoms-in-molecules (QTAIM), noncovalent interaction plot (NCIPlot) index and electron localization (ELF) function (2D and 3D maps) have been used to further characterize the physical nature of the Sb•••Te interactions. The results reported herein suggest that in the Sb•••Te contacts the Te atom acts as σ-hole donor and the Sb as electron density donor.

The effect of heterocyclization of 2-mercaptobenzimidazole on its strength of coordination to iron: A dispersion-corrected DFT study

Benzimidazole derivatives have been widely investigated as corrosion inhibitors due to their unique chemical reactivity with different metal surfaces. Herein, the effect of heterocyclization on corrosion inhibition mechanisms and bonding of two 2-mercaptobenzimidazole derivatives (MBIs) − 2,3-dihydrobenzo[4,5]imidazo[2,1-b]thiazole (2HBIT) and 3,4-dihydro-2H-benzo[4,5]imidazo[2,1-b]thiazole (3HBIT) – with Fe(110) surface was comprehensively evaluated using dispersion-corrected density functional theory (DFT). The interaction energies computed from DFT calculations successfully predicted the experimental inhibition performance. The effect of protonation on the adsorption strength of molecules was also investigated. We have found strong covalent bond formation between S, C, and N atoms of molecules and Fe-atoms. The excellent charge transfer between molecules’ atoms and Fe(110) surface was further confirmed by the projected density of states and electron density difference plots. The adsorption energy of MBI adsorbed on Fe(110) surface was also determined for comparison purposes. This study showed that the heterocyclization of 2-mercaptobenzimidazole increased the charge transfer and bonding between MBIs and the Fe(110) substrate, thereby improving their corrosion inhibition performance.

Maximizing the Carrier Mobilities of Metal-Organic Frameworks Comprising Stacked Pentacene Units.

Charge transport properties of metal–organic frameworks (MOFs) are of distinct interest for (opto)electronic applications. In contrast to the situation in molecular crystals, MOFs allow an extrinsic control of the relative arrangement of π-conjugated entities through the framework architecture. This suggests that MOFs should enable materials with particularly high through-space charge carrier mobilities. Such materials, however, do not yet exist, despite the synthesis of MOFs with, for example, seemingly ideally packed stacks of pentacene-bearing linkers. Their rather low mobilities have been attributed to dynamic disorder effects. Using dispersion-corrected density functional theory calculations, we show that this is only part of the problem and that targeted network design involving comparably easy-to-implement structural modifications have the potential to massively boost charge transport. For the pentacene stacks, this is related to the a priori counterintuitive observation that the electronic coupling between neighboring units can be strongly increased by increasing the stacking distance.

Crystal Engineering of Binary Organic Eutectics: Significant Improvement in the Physicochemical Properties of Polycyclic Aromatic Hydrocarbons via the Computational and Mechanochemical Discovery of Composite Materials

Derivatives of polycyclic aromatic hydrocarbons (PAHs) are widely used in optoelectronic materials. However, the poor solubility of unfunctionalized PAHs represents a challenge for the continued application of these compounds in emerging technologies. For organic compounds bearing one or more functional groups capable of engaging in directional hydrogen or halogen-bonding interactions, the crystal engineering toolkit currently offers many routes for optimizing the solid-state properties of these compounds. Such efforts typically lead to the discovery of periodic crystal forms that display strong adhesive intermolecular forces between the molecular fragments. By contrast, the crystal engineering of organic eutectic composites is relatively unexplored and poorly understood. Here, we report the mechanosynthesis and experimental characterization of the properties of three eutectic composites of pyrene (PYR) and anthracene (ANTH) that were discovered using the coformer bisphenol A (BPA) or phenothiazine (PTZ). The resulting eutectic composites (PYR-BPA, PYR-PTZ, and ANTH-PTZ) display significant melting point depressions ranging from 19 to 51 °C relative to the melting point of the PAH. The equilibrium solubilities of the composite materials were also observed to be 2–5 times greater than that of the PAH. The crystal engineering of eutectic solid forms is currently hampered by the lack of reliable empirical or theoretical tools for predicting their formation. A weighted Monte Carlo simulation was used to estimate the mixing energies and binding modes of a limited set of molecular pairs, leading to temperature-dependent interaction parameters that show promise in the selection of coformers with a high likelihood of forming eutectic composites. Complementary dispersion-corrected density functional theory (DFT-D) calculations on a set of PYR and ANTH composite models reveal that organic eutectic composites are not driven to form on the basis of favorable thermodynamics as evidenced by an average interaction energy of 2.60 kJ mol–1 across the series. Synthon incompatibility and molecular shape mismatch appear to be important factors to consider in targeting eutectic solid forms. This work paves the way for the systematic crystal engineering of organic eutectic solid forms with tunable physicochemical properties using a synergistic computational modeling and mechanosynthesis approach.

Deep Desulfurization with Record SO2 Adsorption on the Metal-Organic Frameworks.

Selective elimination of sulfur dioxide is significant in flue gas desulfurization and natural gas purification, yet developing adsorbents with high capture capacity especially at low partial pressure as well as excellent cycling stability remains a challenge. Herein, a family of isostructural gallate-based MOFs with abundant hydrogen bond donors decorating the pore channel was reported for selective recognition and dense packing of sulfur dioxide via multiple hydrogen bonding interactions. Multiple O···H-O hydrogen bonds and O···H-C hydrogen bonds guarantee SO2 molecules are firmly grasped within the framework, and appropriate pore apertures afford dense packing of SO2 with high uptake and density up to 1.86 g cm-3, which is evidenced by dispersion-corrected density functional theory calculations and X-ray diffraction resolution of a SO2-loaded single crystal. Ultrahigh adsorption uptake of SO2 at extremely low pressure (0.002 bar) was achieved on Co-gallate (6.13 mmol cm-3), outperforming all reported state-of-the-art MOFs. Record-high IAST selectivity of SO2/CO2 (325 for Mg-gallate) and ultrahigh selectivity of SO2/N2 (>1.0 × 104) and SO2/CH4 (>1.0 × 104) were also realized. Breakthrough experiments further demonstrate the excellent removal performance of trace amounts of SO2 in a deep desulfurization process. More importantly, M-gallate shows almost unchanged breakthrough performance after five cycles, indicating the robust cycling stability of these MOFs.

Oriented-Attachment- and Defect-Dependent PbTe Quantum Dots Growth: Shape Transformations Supported by Experimental Insights and DFT Calculations.

High-resolution transmission electron microscopy results reveal that oriented-attachment- and defect-dependent mechanisms rule the size and shape evolution of the monodispersed PbTe quantum dots (QDs). The former is characterized by the growth of quasi-cubic PbTe QDs, which depends on both the geometric constraints imposed by the {200} facets and the defect-free lattice, while the latter one is a defect-dependent mechanism which gives way to the formation of decahedral PbTe QDs (∼6 nm). Experimentally, formaldehyde is an important parameter for the mechanochemical synthesis of monodispersed PbTe QDs, which has not been studied until now. In a theoretical context, Fukui functions reveal that Pb surface atoms are the most reactive sites toward nucleophilic attacks, and the Lowdin charge analysis shows that formaldehyde molecules tend to donate their electron pairs to Pb atoms. Besides, formaldehyde-molecule-on-PbTe adsorption energies (-4.46 to -21.16 kcal mol-1) agree with ligand-surface polar electrostatic interactions. Based on dispersion-corrected density functional theory calculations, PbTe QDs exhibited decahedral and faceted shapes. According to modified Wulff constructions, the decahedral shape is a result of (111) facets (Δγ = -2.79 meV Å-2), whereas the faceted and rounded shapes are due to the interaction of (100), (110), and (111) facets.