Dispersion-corrected Density Functional Theory Research Articles

Adsorption of Carbamazepine in All-Silica Zeolites Studied with Density Functional Theory Calculations.

The anticonvulsant drug carbamazepine (-) is an emerging contaminant of considerable concern due to its hazard potential and environmental persistence. Previous experimental studies proposed hydrophobic zeolites as promising adsorbents for the removal of carbamazepine from water, but only a few framework types were considered in those investigations. In the present work, electronic structure calculations based on dispersion-corrected density functional theory (DFT) were used to study the adsorption of CBZ in eleven all-silica zeolites having different pore sizes and connectivities of the pore system (AFI, ATS, BEA, CFI, DON, FAU, IFR, ISV, MOR, SFH, SSF framework types). It was found that some zeolites with one-dimensional channels formed by twelve-membered rings (IFR, AFI) exhibit the highest affinity towards CBZ. A "good fit" of CBZ into the zeolite pores that maximizes dispersion interactions was identified as the dominant factor determining the interaction strength. Further calculations addressed the role of temperature (for selected systems) and of guest-guest interactions between coadsorbed CBZ molecules. In addition to predicting zeolite frameworks of particular interest as materials for selective CBZ removal, the calculations presented here also contribute to the atomic-level understanding of the interaction of functional organic molecules with all-silica zeolites.

Optimal Binding Affinity for Sieving Separation of Propylene from Propane in an Oxyfluoride Anion-Based Metal-Organic Framework.

Highly efficient adsorptive separation of propylene from propane offers an ideal alternative method to replace the energy-intensive cryogenic distillation technology. Molecular sieving-type separation via high-performance adsorbents is targeted for superior selectivity, but the limit in adsorption capacity remains a great challenge. Here, we report an oxyfluoride-based ultramicroporous metal-organic framework UTSA-400, [Ni(WO2F4)(pyz)2] (pyz = pyrazine), featuring one-dimensional pore channels that can accommodate the propylene molecules with optimal binding affinity while specifically excluding the propane molecules. The exposed oxide/fluoride pairs in UTSA-400 serve as strong functional sites for strengthened propylene-host interactions, accounting for a significantly enhanced propylene uptake, while the propane molecules are excluded due to the regulated host framework dynamics. The strong propylene binding enables near-saturation of propylene in the pore confinement at ambient conditions, leading to full utilization of pore space and superior packing density. Combined in situ infrared spectroscopy measurements and dispersion-corrected density functional theory calculations clearly unveil the nature of boosted host-guest binding. Direct production of polymer-grade (>99.5%) propylene with remarkable dynamic productivity is demonstrated by column breakthrough experiments. This work presents an example of pore engineering with atomic precision to break the trade-off in adsorptive separation through guest binding optimization.

Polymorphs, Solvatomorphs, Hydrate, and Perhydrate of Dabrafenib

Crystal form screening of the anticancer drug dabrafenib (DBF) was performed using a wide range of nonpolar aprotic, polar aprotic, and polar protic solvents. Extensive crystallization in these solvent systems produced three crystal forms (I, II, and III) of the drug, a monohydrate, an isomorphous peroxo solvate, and eight different solvates with ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, 1,1,2,2-tetrachloroethane, tetrachloroethylene, benzene, and anisole of DBF. Surprisingly no solvates were crystallized with the alcohol solvents attempted. The novel crystalline forms were characterized by single-crystal X-ray diffraction (SC-XRD) or structure determination from powder data (SDPD). The neutral drug derived from the mesylate salt of DBF by neutralization (form Ia) and the crystallized form I exhibited almost a similar powder XRD line pattern but their differential scanning calorimetry (DSC) thermograms comparison showed significant differences. Thus, the structure of microcrystalline powder form Ia was solved from SDPD reflections and showed the same molecular packing but different conformational strain compared to form I (structure by SC-XRD). The relative stability of the drug polymorphs was calculated using dispersion-corrected density functional theory with an intramolecular conformational energy correction. The calculations suggest that form II is the most stable polymorph and form III, form I, and form Ia are progressively less stable. Residual water content analysis of the isomorphous peroxosolvate showed that it is a mixed hydrate/peroxosolvate with ∼9.5% water occupancy quantified by 31P nuclear magnetic resonance analysis of the peroxosolvate content using triphenylphosphine oxide. The supramolecular analysis and molecular packing of DBF crystal forms suggest that the molecule has a propensity to form solvates with aprotic solvents and more specifically with chlorohydrocarbons. With its high molecular flexibility, prolific solvate potential, and drug polymorphism, the present work opens the opportunity for further solid-form landscape study of the popular anticancer drug DBF.

Elucidating the Structure–Property Relationship and Ultrafast Exciton/Charge Carrier Dynamics of Layered Cs4CuSb2Cl12Double-Perovskite Microcrystals

In recent times, layered double perovskites have attracted considerable attention due to their nontoxic nature, structural stability in ambient conditions, and ability to tune optoelectronic properties through the interplay between two metal ions. To better comprehend the utility of this promising class of materials to be used as absorber materials in solar cells, it is important to understand the nature of band-gap and excited-state dynamics. In this work, we present a comprehensive study on the microcrystals of Cs4CuSb2Cl12, a relatively new class of double perovskites, which have emerged as a propitious contender. Using dispersion-corrected density functional theory, we study the nature of the band structure and identify the structural and energetic parameters that are also tested experimentally. Further, using femtosecond transient absorption spectroscopy, we show that depending on the excitation wavelength, the excited-state relaxation mechanism involves either excitons or free charge carriers. One crucial observation is the solvent dependence of the relaxation rates of carriers, opening up the possibilities of solvent control of charge carrier dynamics.

Interaction of organic pollutants with TiO2: a density functional theory study of carboxylic acids on the anatase (101) surface

Understanding the interaction of the carboxylic group with TiO2 is crucial for photocatalytic degradation of pollutants, because aromatic molecules containing carboxylic acid groups are among the most common micropollutants. This study investigated the interactions of the anatase TiO2 (101) surface with several aromatic carboxylic acids: benzoic, nicotinic, salicylic and anthranilic acid, using dispersion-corrected density functional theory (DFT) calculations. For all the molecules studied, we found higher stabilities of monodentate adsorbed configurations over bidentate. Dispersion was found to have a significant effect on adsorption energies. In particular, dispersion gave rise to a tilted monodentate adsorption configuration, where adsorption through interfacial covalent and hydrogen bonds was additionally stabilised by dispersion interactions of the aromatic ring with the surface. Comparative calculations using DFT with empirical dispersion correction and van der Waals-corrected functionals found the relative stabilities of adsorbed structures to be independent of the method of describing dispersion. Thermodynamic probabilities of different adsorption configurations were evaluated using the Boltzmann distribution, and the tilted dispersion-stabilised structures were predicted to be by far the most abundant. Finally, the optical absorption of TiO2-acid systems was modelled, and TiO2-aromatic acid complexes were found to have their optical absorption extended into the visible range.

Corrosion inhibition at emergent grain boundaries studied by DFT for 2-mercaptobenzothiazole on bi-crystalline copper

Inhibition of the initiation of intergranular corrosion was modeled at the atomic scale for 2-mercaptobenzothiazole (MBT) adsorbed on a (110)-oriented copper bi-crystal exposing an emergent Σ9 coincident site lattice (CSL) grain boundary (GB) using dispersion-corrected density functional theory (DFT-D). At both isolated molecule and full, dense monolayer coverages, the molecule adsorbed on the grain and GB sites stands perpendicular or tilted with no parallel orientation to the surface being favored. Chemical bonding of the thione and thiolate conformers involves both S atoms or the exocyclic S and N atoms, respectively. The full, dense monolayer is formed with a net gain in energy per surface area, but at the cost of a significant molecule deformation. It significantly enhances the Cu vacancy formation energy at the grain and GB sites, revealing that MBT also inhibits Cu dissolution for the more susceptible GBs with efficiency depending on atomic density of GB emergence.

Exploring the potential use of pristine and metal-encapsulated B36N36 fullerenes in delivery of β-lapachone anticancer drug: DFT approach

Motivated by earlier experimental and theoretical studies on the potential of different nanostructures for drug delivery, the application of B36N36 fullerene is explored as a drug delivery system for anti-cancer β-Lapachone drug based on the dispersion-corrected density functional theory calculations. Results indicate that this fullerene can carry up to six drugs with binding energy per β-Lap of −7.8 kcal/mol in water phase. Furthermore, the influence of alkali or alkaline earth metals (AAM) encapsulation inside the B36N36 fullerene on the β-Lap adsorption performance is studied. The binding energies per β-Lap for AAM-B36N36 endohedral fullerenes are found to be larger than pristine B36N36 in gas and water phases. Therefore, the AAM encapsulation inside the fullerene enhance the adsorption performance of fullerene toward β-Lap adsorption. The desorption mechanisms are examined through pH-dependent and photochemical mechanism of light-triggered. Results indicate that the drug release could be simply occurred in the cancer cells upon protonation is plausible, especially for B36N36 and K-encapsulated B36N36 carries. Obtained data might be helpful for development of boron nitride-based nanocarriers in nanomedicine domain.

Phase Stability, Band Gap Tuning, and Rashba Splitting in Selenium-Alloyed Bournonite: CuPbSb(S1–xSex)3

Recently, bournonite (CuPbSbS3) has been identified as a potential ferroelectric photovoltaic (PV) material with a 1.3 eV band gap, which falls in an appropriate range for single-junction PV devices. Progress in applying bournonite has yielded several studies reporting successful thin-film processing, the most recent of which demonstrated a 2.65% power conversion efficiency for a bournonite-based PV device. In an effort to explore bournonite band gap engineering for PV and other prospective applications (e.g., thermoelectric, spintronic), we here consider the solid-state synthesis of selenium-alloyed bournonite, CuPbSb(S1–xSex)3, across the full range of x (0.0 ≤ x ≤ 1.0) and report phase purity for 0.0 ≤ x ≤ 0.5. We characterize the crystal structure and band gap of the samples using X-ray diffraction and diffuse reflectance spectroscopy, determining a band gap decrease for single-phase samples from 1.25 eV at x = 0.0 to 1.06 eV at x = 0.5. Formation energies determined using dispersion-corrected hybrid density functional theory (DFT) support experimental findings and are consistent with the stability (instability) of the x = 0.5 (x = 1.0) structure relative to starting materials. The computed band structures show a decreasing trend in the band gap with increasing x, again consistent with experiment, with the states at the conduction (valence) band minima (maxima) being principally derived from Pb (S/Se) states. Spin texture analysis and detailed comparison of spin splitting parameters show that Se alloying modifies the band gap while maintaining Rashba spin splitting character within the electronic structure. Rashba splitting is most pronounced for the conduction band minimum along the Γ–X path in the Brillouin zone. Energy separation between spin states is maintained at ΔE ∼0.2 eV for the various Se contents, with σz as the spin direction. A smaller spin splitting occurs along Γ–Z (decreasing value with increasing x), with σx as the spin direction.

Liquid structures of chloroethenes from molecular simulations and electronic structure calculations

The structures of six liquid chloroethenes viz., chloroethene, 1,1-Dichloroethene, cis- and trans-1,2-Dichloroethene, trichloro- and tetrachloroethene, are explored using the all-atom molecular dynamics simulations, molecular simulations with the 3D-reference interaction site model and the Kovalenko-Hirata closure relation (3D-RISM-KH), and dispersion corrected density functional theory. The liquid structures have different local orientations stabilized by possible π-stacking, π⋅⋅⋅Cl, and H⋅⋅⋅Cl intermolecular interactions. The RISM computations and MD simulations are in good agreement with each other, and provided important structural details. The electronic structure calculations support the presence of dimeric structures in the liquid form as well as the findings from the molecular simulations.

Defect properties and solution energies of dopants in NASICON-type LiGe2(PO4)3 solid electrolyte: a first-principles study.

NASICON-type solid electrolytes are suitable choices for solid state batteries considering safer and more stable electrochemical performance compared to other potential solid electrolytes. The present study investigates intrinsic defects and dopant incorporation energetics in the LiGe2(PO4)3 (LGP) electrode material using density functional theory-based calculations. The formation energies of intrinsic defects (Frenkel, Schottky and anti-sites) indicate that Li Frenkel pair formation is the most energetically feasible process. With an aim to improve the lithium ion conductivity and chemical stability by suitable doping, solution energies are calculated for various trivalent (M3+ = B3+, Al3+, Ga3+, Sc3+, In3+, Y3+, Gd3+, La3+) and tetravalent (M4+ = Si4+, Ti4+, Sn4+ and Zr4+) ions substituted at the Ge4+ site. The most favourable trivalent and tetravalent dopants are Al3+ and Ti4+, respectively. The changes in lattice parameters with doping are correlated with channel/bottleneck size for Li+ migration. Alkali atom doping at the Li+ site is energetically favourable whereas alkali-earth doping at the Li+ site is not. Analysis based on Bader charges and density of states delineates changes in chemical interactions between the dopant atoms and the host LGP.

Experimental and computational study on the influence of cobalt substitution on the structural, impedance, electronic, magnetic, and optical properties of pseudobrookite-structured Fe2TiO5.

We report on how Co substitution of the Fe sites of pseudobrookite (Fe2TiO5) influences the crystal structure, high-temperature electric permittivity, impedance, electronic structure, magnetic, and optical properties via experimental and theoretical investigations. The pseudobrookite phase contains two types of octahedral sites, Fe atoms reside on type of the sites while Ti on the others and replacing Fe with Co can have a huge influence on one or more physical properties that can render the material more useful for solar energy applications. X-ray diffraction and high-temperature electric permittivity/impedance were the experimental tools used. A temperature range of 20-300 °C and a frequency range of 100 Hz to 1 MHz were used for studying various types of relaxation mechanism via impedance analysis, including grains, grain boundaries, and interfacial effects. To explore the electronic structure, magnetic, and optical properties from first principles, dispersion-corrected density functional theory (PBE-D2/U) was employed. The structure as well as the electric impedance properties are impacted slightly by the Co substitution of Fe in Fe2TiO5 whereas the electronic structure and magnetic properties are influenced significantly. The bandgap is reduced slightly and the average magnetic moment per Fe ion is reduced upon Co substitution of Fe in Fe2TiO5.

Carbon vacancy-assisted stabilization of individual Cu5 clusters on graphene. Insights from ab initio molecular dynamics.

Recent advances in synthesis and characterization methods have enabled the controllable fabrication of atomically precise metal clusters (AMCs) of subnanometer size that possess unique physical and chemical properties, yet to be explored. Such AMCs have potential applications in a wide range of fields, from luminescence and sensing to photocatalysis and bioimaging, making them highly desirable for further research. Therefore, there is a need to develop innovative methods to stabilize AMCs upon surface deposition, as their special properties are lost due to sintering into larger nanoparticles. To this end, dispersion-corrected density functional theory (DFT-D3) and ab initio molecular dynamics (AIMD) simulations have been employed. Benchmarking against high-level post-Hartree-Fock approaches revealed that the DFT-D3 scheme describes very well the lowest-energy states of clusters of five and ten atoms, Cu5 and Cu10. AIMD simulations performed at 400 K illustrate how intrinsic defects of graphene sheets, carbon vacancies, are capable of confining individual Cu5 clusters, thus allowing for their stabilization. Furthermore, AIMD simulations provide evidence on the dimerization of Cu5 clusters on defect-free graphene, in agreement with the ab initio predictions of (Cu5)n aggregation in the gas phase. The findings of this study demonstrate the potential of using graphene-based substrates as an effective platform for the stabilization of monodisperse atomically precise Cu5 clusters.

Effects of hydrostatic pressure on structural, mechanical, and electronic properties of energetic molecular perovskite (C6H14N2)(NH2NH3)(ClO4)3: a DFT-D insight

The structural, mechanical, and electronic properties and intermolecular interactions of (C6H14N2)(NH2NH3)(ClO4)3 at pressures up to 40 GPa have been investigated in detail for the first time by using dispersion-corrected DFT.

Analysis of intermolecular interactions of n-perfluoroalkanes with circumcoronene using dispersion-corrected DFT calculations: comparison with those of n-alkanes.

Understanding the interactions between the adsorbate and substrate is critical in basic and advanced scientific fields, including the formation of well-organised nanoarchitectures via self-assembly on surfaces. In this study, the interactions of n-alkanes and n-perfluoroalkanes with circumcoronene were studied using dispersion-corrected density functional theory calculations as models of their adsorption on graphite. The interactions of n-perfluoroalkanes with circumcoronene were significantly weaker than those of the corresponding n-alkanes, e.g. the calculated adsorption energies of n-perfluorohexane and n-hexane were -9.05 and -13.06 kcal mol-1, respectively. The dispersion interactions were the major source of attraction between circumcoronene and the adsorbed molecules. Larger steric repulsion of n-perfluoroalkanes compared to those of n-alkanes increased their equilibrium distances from circumcoronene and decreased the dispersion interactions, resulting in weaker interactions. The interactions between two adsorbed n-perfluorohexane molecules and those of n-hexane molecules were -2.96 and -2.98 kcal mol-1, respectively, which are not negligible in the stabilisation of adsorbed molecules. The geometries of adsorbed n-perfluoroalkane dimers revealed that the equilibrium distance between two n-perfluoroalkane molecules did not match the width of the six-membered rings in circumcoronene, in contrast to that between n-alkanes. The lattice mismatch also destabilised the adsorbed n-perfluoroalkane dimers. The difference in the adsorption energy between flat-on and edge-on orientations of n-perfluorohexane was smaller than that of corresponding n-hexane.

Infrared spectrum of the 1-cyanoadamantane cation: evidence of hydrogen transfer and cage-opening upon ionization.

The radical cations of diamondoids are important intermediates in their functionalization reactions and are also candidates as carriers for astronomical absorption and emission features. Although neutral diamondoids have been studied extensively, information regarding their radical cations is largely lacking, particularly for functionalized diamondoid derivatives. Herein, we characterize the structure of the 1-cyanoadamantane radical cation (C10H15CN+, AdCN+) using infrared photodissociation (IRPD) spectroscopy of mass selected AdCN+N2 clusters in the XH stretch range (2400-3500 cm-1) and dispersion-corrected density functional theory calculations (B3LYP-D3BJ/cc-pVTZ). A group of three distinct CH stretch bands are observed in the 2800-3000 cm-1 range, in addition to a highly redshifted absorption at 2580 cm-1 attributed to the acidic CH proton predicted by calculations. An unexpected broad absorption peaking at 3320 cm-1 is also detected and assigned to an NH stretch mode based on its width and frequency. Calculations indicate that hydrogen atom transfer (HAT) from the adamantyl cage (C10H15, Ady) to the N atom of the CN group yields lower energy structures, with an open-cage isomer exhibiting such hydrogen transfer being the global minimum on the potential energy surface. The energy barriers involved in the formation of this open-cage isomer are also lower than those calculated for generation of the analogous open-cage 1-amantadine cation isomer which has previously been identified by IRPD. The combined consideration of IRPD spectra and calculations indicates a major population of the nascent canonical closed-cage isomer and a smaller population of the global minimum isomer featuring both cage-opening and hydrogen transfer.

Strengthened cooperativity of DNA-based cyclic hydrogen-bonded rosettes by subtle functionalization.

Cooperative effects cause extra stabilization of hydrogen-bonded supramolecular systems. In this work we have designed hydrogen-bonded rosettes derived from a guanine-cytosine Janus-type motif with the aim of finding a monomer that enhances the synergy of supramolecular systems. For this, relativistic dispersion-corrected density functional theory computations have been performed. Our proposal involves a monomer with three hydrogen-bonds pointing in the same direction, which translates into shorter bonds, stronger donor-acceptor interactions, and more attractive electrostatic interactions, thus giving rise to rosettes with strengthened cooperativity. This newly designed rosette has triple the cooperativity found for the naturally occurring guanine quadruplex.

Potential of nanostructured carbon materials for iodine detection in realistic environments revealed by first-principles calculations.

In the context of effective detection of iodine species (I2, CH3I) formed in nuclear power plants and nuclear fuel reprocessing facilities, we perform a comparative study of the potential sensing performance of four expectedly promising 2D materials (8-Pmmn borophene, BC3, C3N, and BC6N) towards the iodine-containing gases and, with the view of checking selectivity, towards common inhibiting gases in the containment atmosphere (H2O and CO), applying methods of dispersion-corrected density functional theory with periodic boundary conditions. A covalent bond is formed between the CO molecule and boron in BC3 or in 8-Pmmn borophene, compromising the anticipated applicability of these materials for iodine detection. The presence of nitrogen atoms in BC6N-2 prevents the formation of a covalent bond with CO; however, the closeness of adsorption energies for all the four gases studied does not distinguish this material as specifically sensitive to iodine species. Finally, the energies of adsorption on C3N yield a significant and promising discrimination between the adsorption energies of (I2, CH3I) vs. (CO, H2O), revealing possibilities for this material's use as an iodine sensor. The conclusions are supported by simulations at finite temperature; underlying electronic structures are also discussed.

Location of Artinite (Mg2CO3(OH)2·3H2O) within the MgO-CO2-H2O system using ab initio thermodynamics.

The MgO-CO2-H2O system have a variety of important industrial applications including in catalysis, immobilisation of radionuclides and heavy metals, construction, and mineralisation and permanent storage of anthropogenic CO2. Here, we develop a computational approach to generate phase stability plots for the MgO-CO2-H2O system that do not rely on traditional experimental corrections for the solid phases. We compare the predictions made by several dispersion-corrected density-functional theory schemes, and we include the temperature-dependent Gibbs free energy through the quasi-harmonic approximation. We locate the Artinite phase (Mg2CO3(OH)2·3H2O) within the MgO-CO2-H2O phase stability plot, and we demonstrate that this widely-overlooked hydrated and carbonated phase is metastable and can be stabilised by inhibiting the formation of fully-carbonated stable phases. Similar considerations may apply more broadly to other lesser known phases. These findings provide new insight to explain conflicting results from experimental studies, and demonstrate how this phase can potentially be stabilised by optimising the synthesis conditions.

Theoretical understanding of stability of mechanically interlocked carbon nanotubes and their precursors.

Dispersion-corrected DFT calculations were performed on (a,a) nanotubes (a = 5-10) attached by a U-shaped functional group consisting of p-xylene-linked double 9,10-di(1,3-dithiol-2-ylidene)-9,10-dihydro anthracene terminated by CnH2n chains (n = 6, 8, and 9), and their ring-closing macrocycles containing tubes. The reactant precursors and macrocycles are denoted by UP-n-(a,a) and (a,a)@Cycle-n, respectively. We found that UP-n-(a,a) are energetically preferable relative to the dissociation limit toward a U-shaped functional group (UP-n) and a tube (initial state) due to the attractive CH-π and π-π interactions. The attractive interactions are enhanced by increasing the tube diameters and CnH2n chain lengths because UP-n structures can be easily adjusted to interact with the tubes. The stability of (a,a)@Cycle-n and related (a,b)@Cycle-n is sensitive to tube diameters due to the restriction of ring structures. When diameter differences between a Cycle-n and a tube (D-d) are larger than 5 Å, (a,a)@Cycle-n plus C2H4 are energetically preferable relative to the initial state. However, the (a,a)@Cycle-n plus C2H4 byproduct is always energetically unstable relative to UP-n-(a,a). The DFT calculations found that the energy differences were low at D-d values ranging from 7 to 8 Å, explaining the tube-diameter-selective formation of the mechanically-interlocked tubes, observed experimentally.

Design of transition metal complexes containing a P-E radical motif.

Recently, we have synthesized phosphane W(CO)5 complexes containing a P-O-TEMP ligand motif as bench-stable precursors of thermally accessible phosphanoxyl complex radicals possessing a ligand with a P-O˙ group. In this work, extensive dispersion-corrected DFT calculations are used to explore both W(CO)5 and Fe(CO)4 phosphane complexes containing the P-E-TEMP ligands (E = O, S, NMe, and PMe) in order to reach thermally accessible radicals with a P-E˙ motif. Moreover, a more general single-electron transfer (SET) oxidation approach to synthesize such P-E˙ radicals via anionic precursors is disclosed. Furthermore, the tendencies for self-trapping and prototropic reactions of such radical complexes have been studied for the first time. Electronic structures and potential conversions of such P-E˙ radicals are discussed, thus paving the way to a broad range of transition metal radical complexes, including potential thermal radical initiators.