Density functional study of small bimetallic Ag–Pd clusters

The geometric and electronic properties of small Ag_mPd_n clusters with m + n = 2–5 are studied within the framework of density functional theory in conjunction with two hybrid and one GGA exchange–correlation functional. For every composition, the global minimum is identified by using geometry optimization for a collection of initial structures. Results indicate that, for bimetallic tetramers and pentamers, the clusters shift from two-dimensional to three-dimensional structures with the addition of a second Pd atom. Ag₂Pd₂ is identified as the most stable tetramer by the calculation of the excess energy and second energy difference of bimetallic clusters. Concerning the fragmentation channels it is seen that the most favourable route in the majority of cases is via the evaporation of a single atom. Density of states calculations reveal that the increase of Pd content depletes the isolated s states close to the Fermi level, while at the same time shifts the d states to higher energies.     

The importance of Colle–Salvetti for computational density functional theory

The purpose of this presentation is to show the importance of the Colle–Salvetti (Theor Chim Acta 37:329, 1975) paper in the development of modern computational density functional theory. To do this we cover the following topics (1) the Bright Wilson understanding (2) the Kohn–Sham equations (3) local density exchange (4) the exchange-hole (5) generalised gradient approximation for exchange (Becke and Cohen) (6) left–right correlation and dynamic correlation (7) the development of the Lee–Yang–Parr dynamic correlation functional from the Colle–Salvetti paper (8) the early success of GGA DFT. Finally we observe that the the BLYP and OLYP exchange-correlation functionals are not semi-empirical; this may explain their great success.     

The interaction between silica flat substrate and functional group–modified nanoparticles

Inspired by nature, the research of functionalized nanoparticles and nanodevices has been in-depth developed in recent years. In this paper, we theoretically studied the interaction between functional polyelectrolyte brush layer–modified nanoparticles and a silica flat substrate. Based on the Poisson–Nernst–Planck equations, the mathematical model is established. The changes of the volume charge density and electric field energy density when the nanoparticle interacts with the silica flat substrate under multi-ions regulation were investigated. The results show that when there is a strong interaction between the silica flat substrate and nanoparticles, such as the distances between the nanoparticle and silica flat substrate, which are 2 or 5 nm, the isoelectric point shift under the influence of silica flat substrate and the total charge density in the brush layer is jointly controlled by the cations in the solution and the volume charge density of the brush layer. With the increase of the distances between the nanoparticle and silica flat substrate, the regulation of the volume charge density of the brush layer dominates. These results will provide guidance for the movement mechanism of functionalized nanoparticles in silica nanochannels.     

Azo-pyrene–based fluorescent sensor of reductive cleavage of isomeric azo functional group

In this study we investigated the reductive azo cleavage of an azo compound presenting a pyrene fluorophore (Azo-py). Because of dramatic changes in its fluorescence, Azo-py could be used as a monitoring system for the reductive azo cleavage. Electron transfer from the pyrene unit to the azo moiety induced fluorescence quenching; this quenched fluorescence was recovered after the reductive azo cleavage. IR and NMR spectroscopy were used to study the various structural states. The rate of reductive cleavage of the azo compound, determined through fluorescence monitoring, depended on its structural state: the cleavage of trans-Azo-py was much faster than that of the cis-Azo-py. Furthermore, the Azo-py fluorophore was highly sensitive to the presence of zinc, but not other metal compounds, and the pH.     

Sol–gel technology for functional finishing of PES fabric by stimuli-responsive microgel

The possibility of incorporating a stimuli-responsive microgel into a silica matrix by the sol–gel method was studied. This method allows the preparation of a novel class of functional finishes for textile material modification, which is aimed at the creation of simultaneous stimulus-responsive behaviour and functional protective properties. Using a pad-dry-cure method, a thermo- and pH-responsive microgel (PNCS) based on poly-(N-isopropylacrylamide) (poly-NiPAAm) and chitosan was embedded into a silica matrix on a previously activated polyester (PES) fabric. The matrix was composed of a model sol–gel precursor, vinyltrimethoxysilane (VTMS), in combination with hydrophilic fumed silica nanoparticles (SiO₂). Functionalized PES fabric samples were characterised by determining the morphological and chemical properties using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The stimuli (temperature and pH) responsiveness of the functionalized PES fabric was established by measuring its porosity, wicking ability, moisture content, drying rate, water vapour transmission rate and water uptake. In order to assess the washing fastness of the surface modifying systems, the tests were done before and after five consecutive washings. The results showed that sol–gel technology is an appropriate method for the incorporation of PNCS microgel on PES fibre surface. Because of the elasticity of the sol–gel matrix, the VTMS/SiO₂ polysiloxane film had no adverse influence on the swelling/deswelling effect of the PNCS microgel, thus retaining and even enhancing its stimulus response.     

A variational approach to the Dirichlet–Gabor wavelet‐distributed approximating functional

We show that the Dirichlet–Gabor waveletdistributed approximating functional (DAF) can be derived from the same variational principle used to obtain noninterpolating waveletDAFs (such as the Hermite DAF). This variational approach for such interpolating DAFs complements the original viewpoint that they are generated by regularizing interpolating shells or through twoparameter Dirac delta sequences.     

Structure–antioxidant activity relationships of dendrocandin analogues determined using density functional theory

Structural Chemistry - Quantum-chemical calculations based on the density functional theory (DFT) at the B3LYP/6–311?+?+?G(2d,2p)//B3LYP/6–31G(d,p) level were employed...     

Synthesis and properties of functional dyes with squaraine–naphthalene diimide hybrid structure

Naphthalene diimides (NDIs) are promising candidate for electron acceptors due to their low-lying HOMOs and LUMOs. The functinalization of soluble NDIs at the 2,6-position affects the absorption and electrochemical properties. In this study, NDI-based hybrid dyes NDI-SQ-A, B fused with squaraine chromophore were designed and synthesized in order to elucidate the effects of the substitution on their optical and electrochemical properties. These dyes were successfully synthesized by Stille coupling reactions using 3-stannylcyclobutenediones and brominated NDI derivative, followed by a condensation reaction. DFT calculation predicts that the present dyes adopt distorted structures coming from a steric hindrance between semisquaraine and NDI moieties. The hybrid dyes show low-lying LUMOs due to the introduction of electron-deficient NDI moiety and broad absorption spectra in the far-red region. The absorption spectra of their thin films were bathochromically shifted relative to those in solution, indicating that hybrid dyes formed J aggregates.     

Bioinorganic chemistry of molybdenum and tungsten enzymes: A structural–functional modeling approach

Chemical approaches toward the bioinorganic chemistry of molybdenum and tungsten enzymes had been either biomimetic (structural modeling) or bioinspired (functional modeling). Among the dithiolene type of ligands, bdt (1,2-benzene dithiolate) and related aromatic molecules as model ene–dithiolene ligands were used to react with pre-designed molybdenum complexes in organic solvents. Whereas in the alternative approach mnt (maleonitrile dithiolate) is used to mimic the ligand backbone of the central atom in the active sites of these enzymes using molybdate or tungstate as the metal source in water. Structural–functional models are known for some selected enzymes, namely, sulfite oxidase, aldehyde ferredoxin oxidoreductase, tungsten formate dehydrogenase, acetylene hydratase, polysulfide reductase and dissimilatory nitrate reductase. The protocols and methodologies adopted to achieve these model systems compared with various other model systems described in this review give testimony to chemist's ability, through chemical manipulations, to achieve the model systems which may potentially serve as structural–functional mimics of natural enzyme systems.     

Electrocatalytic oxidation of formic acid on functional MWCNTs supported nanostructured Pd–Au catalyst

In this work, PdAu nanocatalysts with different weight ratio of Pd and Au supported on functional multi-walled carbon nanotubes (f-MWCNTs) were prepared, and their electrocatalytic activity for the oxidation of formic acid was also studied. The electrocatalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical results showed that the 4Pd1Au/f-MWCNTs (by weight) catalyst, exhibited distinctly higher activity and better stability in formic acid electrooxidation than the Pd/f-MWCNTs catalyst. The Nano-Au improves potentially the performance of Pd-based electrocatalysts for the direct formic acid fuel cells (DFAFCs).     

Spin-forbidden CO binding to iron–sulfur cluster-free hydrogenase: A density functional study

Spin-forbidden CO binding to the iron–sulfur cluster-free hydrogenase (Hmd) is studied by the DFT calculation. The result shows that the surface of the triplet causes a PHmd–CO minimum and that ^3,5MECP is the lowest energy path to PHmd–CO. It is found that this CO binding involves a low barrier of 0.931 kcal/mol because of the need to change from a bound triplet state to the Hmd quintet ground state.     

Adiabatic integration formula for the correlation energy functional of the Hartree–Fock density

An adiabatic integration formula for the quantum chemistry correlation energy functional of the Hartree–Fock density, E _c ^QC[n], is presented. The functional E _c ^QC[n] is meant to be added to the completed Hartree–Fock energy to produce the exact ground-state energy of the system under consideration. The initial slope of the integrand in this connection formula is identified as a second-order energy and an explicit expression for the initial slope of the integrand is presented. Our expression should be useful for arriving at new improved approximations to E _c ^QC[n]. Previous numerical results by Huang and Umrigar (1997) Phys Rev A 56:290, for two-electron densities are proved, and a generalization to more than two electrons is presented. Results obtained by means of the present density functional theory correlation energy functionals, when used to approximate the initial slope in our adiabatic integration formula for E _c ^QC[n], are compared against exact numbers. Received: 10 September 1998 / Accepted: 3 February 1999 / Published online: 21 June 1999     

Coating functional sol–gel films inside horizontally-rotating cylinders by rimming flow/state

The fabrication of uniform sol–gel coatings with embedded functional nanomaterials inside cylinders requires detailed understanding of the gelation behavior. For sol–gel systems the viscosity is a function of gelation time that affects sol–gel coatings on the inside of a slowly, horizontally rotating cylinder. Therefore the angular velocity has to be adjusted to this time dependence. The higher the viscosity the more liquid is dragged along with the moving cylinder wall while the balance of gravity and drag limits the layer thickness. In addition, inertial forces and surface tension can create instabilities within the coated layer. Here, we show that it is important to suppress these instabilities by transitioning the viscous sol directly to a velocity that allows for the formation of an almost uniform layer. In this regime, which is the so-called rimming state, the recirculation of the gel precursor solution is strongly reduced which allows to fabricate coatings with shear sensitive sol–gel chemistries. Here, we tested this approach with 4 different aerogel systems, with low-density CH-based-, TiO₂-, SiO₂- and Fe₂O₃-aerogels, that represent a wide variety of different sol–gel behaviors. We show that the required rotational velocities for these aerogel systems can be predicted with a simple analytical approximation, and we performed computational fluid dynamics simulations to predict local shear and thickness uniformity.     

Surface-enhanced Raman scattering of M2–pyrazine–M2 (M = Cu,Ag, Au): Analysis by natural perturbation orbitals and density functional theory functional dependence

Here, we propose a new method to analyze various electronic properties of molecules based on natural perturbation orbitals (NPOs). We applied the proposed method to chemical enhancement of the surface-enhanced Raman scattering (SERS) intensity of M₂–pyrazine–M₂ (M = Cu, Ag, Au) complexes. The SERS intensity can be effectively decomposed into the contributions of four NPO pairs (1σ–1σ*, 2σ–2σ*, 1π–1π*, and 2π–2π*), so NPO analysis makes the SERS intensity much easier to understand than by conventional canonical molecular orbitals. Moreover, we analyzed the dependence of the density functional theory functional on the SERS intensity. For the Ag₂–pyrazine–Ag₂ complex, the BP86 functional overestimates the Raman intensity by about 23 times compared with coupled-cluster singles and doubles level of theory, while the CAM-B3LYP functional gives moderately accurate values. This overestimation arises from the inaccuracy of the energy derivative along the normal vibrational mode.     

Identifying promising metal–organic frameworks for heterogeneous catalysis via high-throughput periodic density functional theory

Metal–organic frameworks (MOFs) are a class of nanoporous materials with highly tunable structures in terms of both chemical composition and topology. Due to their tunable nature, high-throughput computational screening is a particularly appealing method to reduce the time-to-discovery of MOFs with desirable physical and chemical properties. In this work, a fully automated, high-throughput periodic density functional theory (DFT) workflow for screening promising MOF candidates was developed and benchmarked, with a specific focus on applications in catalysis. As a proof-of-concept, we use the high-throughput workflow to screen MOFs containing open metal sites (OMSs) from the Computation-Ready, Experimental MOF database for the oxidative C—H bond activation of methane. The results from the screening process suggest that, despite the strong C—H bond strength of methane, the main challenge from a screening standpoint is the identification of MOFs with OMSs that can be readily oxidized at moderate reaction conditions. © 2019 Wiley Periodicals, Inc.     

A density functional theory investigation of CrSin (n=1–6) clusters

Clusters of the form CrSi_n (n=1–6) were investigated computationally using a density functional approach. In particular, geometry optimizations were carried out under the constraint of well-defined point group symmetries at the B3LYP level employing a pseudopotential method in conjunction with double zeta basis sets. In this article, the resulting total energies, Mulliken atomic net populations, overlap populations, fragmentation energies and geometries of CrSi_n (n=1–6) are presented and discussed, together with natural populations and natural electron configurations. In addition, we comment on the charge transfer within the clusters. From this analysis, the 3d orbital of the Cr atom in CrSi_n (n=1–6) cluster absorbs electrons. From this tendency, conclusions are drawn with respect to the electronic populations and the chemical bond between Si and Cr as well as Si and Si.     

Degradation mechanism and increased stability of chitosan-based hybrid scaffolds cross-linked with nanostructured carbon: Process–structure–functional property relationship

The degradation behavior of porous scaffolds plays an important role in the synthesis of new tissue. In this study, three-dimensional hybrid porous scaffolds of chitosan (CS) comprised of nanostructured carbon (graphene oxide (GO) and single-walled carbon nanohorns (SWCNH)) were prepared by freeze-drying method. In-vitro degradation behavior of scaffolds was investigated up to 8 weeks in phosphate buffer saline (PBS) solution at 37 °C. The characteristics of scaffolds explored as a function of degradation time include crystalline structure, pore morphology, molecular weight, and wet/dry weight. The pH value of the PBS solution during degradation was also monitored. The study demonstrates for the first time that hybrid chitosan scaffolds with nanostructured carbon (GO and SWCNH) are potentially more stable than pure chitosan scaffolds during the time period required for tissue regeneration. The stability of hybrid scaffolds is attributed to nanostructured carbon that was processed with the objective that it is present in a robust manner via a highly cross-linked dense network structure. The chemical structure of chitosan was disrupted within a short period of two weeks, while disruption occurred in hybrid scaffolds after eight weeks. This was accompanied by a weight loss of ∼28% in pure chitosan and ∼20% in hybrid scaffolds. Furthermore, the degraded products were of low molecular weight in pure chitosan and high molecular weight in hybrid chitosan scaffolds. This led to significant decrease in the pH of solution to ∼6.2 in pure chitosan and to ∼7.2 in hybrid scaffolds. The observations clearly underscore that the introduction of GO and SWCNH via cross-link mechanism in CS is a potentially viable approach to tune the degradation rate of hybrid scaffolds in tissue engineering.     

Recent advances of functional gels controlled by pillar[n]arene-based host–guest interactions

Functional gels fabricated from supramolecular host–guest interactions exhibit outstanding characteristics including stimuli-responsiveness, self-healing and adaptability. Pillar[n]arenes are new generation of supramolecular macrocyclic host, which displayed excellent host–guest recognition properties. In the last few years, pillar[n]arene-based gels that include both hydrogels and organogels have been attracted more and more attention. In this digest, the recent advances in this field are reviewed, with special emphasis on the multistimuli responsive pillar[n]arene gels. It is anticipated that more and more pillar[n]arenes-based gel materials with smart properties will be developed in the near future.     

Density functional theory and topological analysis on the hydrogen bonds in cysteine–propanoic acid complexes

The complexes formed via hydrogen bonding interactions between cysteine and propanoic acid have been studied at the density three-parameter hybrid functional DFT-B3LYP/6-311++G(d,p) level regarding their geometries, energies, vibrational frequencies, and topological features of the electron density. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis was employed to elucidate the interaction characteristics in cysteine–propanoic acid (Cys–Prop) complexes. More than 10 kinds of hydrogen bonds (H-bonds) including intra- and inter-molecular H-bonds have been found in Cys–Prop complexes. The results show that both the strength of H-bonds and the deformation are important factors for the stability of Cys–Prop complexes. The strongest H-bonds (O2H^A···O1^B and O2H^A···O1^B) exist in the most stable Cys–Prop complex. The stronger H-bonds formed between hydroxyl and O (or N) atom usually stronger than those involve C (or S) atom. Relationships between the electron density (ρ) of BCP and H-bond length as well as the Fock matrix element (F _ij) has also been investigated and used to study the nature of H-bonds. Moreover, the results show that the change of the bond length linearly correlates with the corresponding frequency shift.     

Catalytic effect of molecular iodine in Diels–Alder reaction: a density functional theory study

We explore here the feasibility of employing molecular iodine as Lewis acid catalyst for Diels–Alder (DA) reaction using conceptual density functional theory (DFT) based reactivity indices and transition state analysis at the DFT (B3LYP)/6-31G(d) level of theory. Catalytic effect of iodine is probed using reactivity indices considering six different substituents for the diene at the 2-position and five different substituents at the 1-position of the olefinic dienophile. Comparison of HOMO diene–LUMO dienophile gap between the catalyzed and uncatalyzed processes confirms catalytic effect of iodine in DA reaction. Mechanistic details of both the uncatalyzed and the iodine catalyzed processes is achieved through transition state analysis for four possible stereoisomeric reactive channels with respect to isoprene–acrolein model reaction. A significant cutback in activation barrier is observed in presence of iodine. Influence of iodine on regioselectivity of the reaction and asynchronicity of bond formation is analyzed using local version of the HSAB principle and philicity index.