DFT Study on the Spin States of Polyaniline-3d Transition-Metal (Sc-Zn) Composites and Their Sensing Application to Detect Chemical Warfare Agents.

Organic-inorganic composite materials, combining polymers with transition metal (TM) atoms based on PAni and 3d TMs, have been designed and investigated in various spin states by performing density functional calculations. These designed composites were analyzed for their stability in different spin states as well as for their calculated electronic properties, including binding energies, frontier molecular orbitals, and dipole moments. Additionally, 3D isosurfaces and 2D scattered plots of reduced density gradient as a function of (sign λ2)ρ provide insights into the noncovalent interactions between the composite units. The most stable Mn@PAni composite has been assessed as a sensing material for chemical warfare blood agents (HCN, NCCl, NCBr, NCCN, and AsH3) using density functional-based calculations. The reduced band gap and significant red/blue shift in the UV-vis spectra obtained through TDDFT calculations underline the selectivity and efficiency of the Mn@PAni composite toward different analytes.

Ligand and Substituent Effect on Regium-π Bonding in Cu and Ag π-Conjugated Complexes: A Density Functional Study.

Density functional theory investigation of regium (Rg)-π bonding using the RgL-X model system, where Rg = Cu and Ag; L = CN, NO2, and OH; X = π-conjugated system (benzene, cyanobenzene, benzoic acid, pyridine, 2-methoxy aniline, 1,4-dimethoxy benzene, and cyclophane), has been performed. Conclusive evidence of the Rg-π bond has been provided by analysis of molecular electrostatic potential surfaces, Rg-π bond length, interaction energy (ΔE), second-order perturbation energy (E2), charge transfer (Δq), quantum theory of atom in molecules, and noncovalent interaction plots for 42 structural arrangements with varying ligands and the substituted aromatic ring. The Rg-π bond length in the optimized model systems varies from 2.03 to 2.12 Å in Cu complexes (1-21) and from 2.26 to 2.38 Å in Ag complexes (22-42) at the PBE0-D3 functional. While the ligand (L) attached to the Rg metal has a bargaining effect on the strength of the Rg-π bond (in the order of -OH > -CN = -NO2), the π-conjugated systems have a diminutive effect. Two X-ray crystal structures (CUCSOI and AHIDQU) having the Rg-π bond, accessed from Cambridge Crystallographic Data Centre (CCDC), are discussed here to signify the influence of Rg-π bonding on the crystal structure.

Properties of Naked Silver Clusters with Up to 100 Atoms as Found with Embedded-Atom and Density-Functional Calculations.

The structural and energetic properties of small silver clusters Agn with n = 2-100 atoms are reported. For n = 2-100 the embedded atom model for the calculation of the total energy of a given structure in combination with the basin-hopping search strategy for an unbiased structure optimization has been used to identify the energies and structures of the three energetically lowest-lying isomers. These optimized structures for n = 2-11 were subsequently studied further through density-functional-theory calculations. These calculations provide additional information on the electronic properties of the clusters that is lacking in the embedded-atom calculations. Thereby, also quantities related to the catalytic performance of the clusters are studied. The calculated properties in comparison to other available theoretical and experimental data show a good agreement. Previously unidentified magic (i.e., particularly stable) clusters have been found for n>80. In order to obtain a more detailed understanding of the structural properties of the clusters, various descriptors are used. Thereby, the silver clusters are compared to other noble metals and show some similarities to both copper and nickel systems, and also growth patterns have been identified. All vibrational frequencies of all the clusters have been calculated for the first time, and here we focus on the highest and lowest frequencies. Structural effects on the calculated frequencies were considered.

Cooperative Effect of Noncovalent Interactions on Tetrel Bonding in Halogenated Silanes.

Tetrel bond, a weak noncovalent interaction between the σ-hole of a Group IV element (silicon in our case) and the cloud of an electronegative element (oxygen in our case) is the focus of this work. The percentage strengthening of tetrel bond has been investigated by optimizing 16 binary complexes of halogenated silane and water of general formula SiXn H4-n -H2 O and 16 ternary complexes, of general formula NaX-SiXn H4-n -H2 O, where X=F, Cl, Br and I and n=1, 2, 3 and 4 at various levels of theory defined within the formalism of density functional theory (DFT). With the addition of NaX, tetrel bond between Si and O in SiXn H4-n -H2 O gets strengthened up to 49 %, owing to cooperativity effect exerted by hydrogen bonding between X and H in the ternary complex NaX-SiXn H4-n -H2 O. In the series of complexes studied here, overall stabilization due to cooperativity lies between 10 kJ/mol to 170 kJ/mol. This large extent of reinforcement due to cooperativity has never been showcased before. The exceptional stabilization and reinforcement owe its genesis to the transformation of the ternary complex into a cluster orchestrated by the H-bonding in most of the cases and covalent bonding in few of the cases.

First Principle Studies to Tailor Graphene Through Synergistic Effect as a Highly Efficient Electrocatalyst for Oxygen Evolution Reaction.

The Oxygen Evolution Reaction (OER) is one of the major roadblocks for electrocatalytic oxidation of water (water splitting) and for designing efficient metal-air batteries. Herein, we present a comprehensive study to design graphene based efficient electrocatalyst, modified by doping with main group elements Al, Si, P, S and co-doping with B and N, for OER using DFT computations. Four elementary steps in the OER reaction have been traced, free energy change for each elementary step was calculated considering thermodynamic corrections. Out of all the doped models, S doped graphene shows maximum efficiency that was further enhanced by adjusting the concentration of codopants B and N around the active dopant site. Our results show that synergy between codopants B and N and dopant S atom leads to high electrocatalytic efficiency of modified graphene towards OER and brings down the overpotential to as low as 0.44 V.

Kinetics and Thermodynamics of CO Oxidation by (TiO2)6.

Molecular level insights into the mechanism and thermodynamics of CO oxidation by a (TiO2)6 cluster have been obtained through density functional calculations. Thereby, in this study, as an example, two different structural isomers of (TiO2)6 are considered with the purpose of understanding the interplay between local structure and activity for the CO oxidation reaction. Active sites in the two isomeric forms were identified on the basis of global and local reactivity descriptors. For the oxidation of CO to CO2, the study considered both sequential and simultaneous adsorption of CO and O2 on (TiO2)6 cluster through the ER and LH mechanisms, respectively. Three different pathways were obtained for CO oxidation by (TiO2)6 cluster, and the mechanistic route of each pathway were identified by locating the transition-state and intermediate structures. The effect of temperature on the rate of the reaction was investigated within the harmonic approximation. The structure-dependent activity of the cluster was rationalized through reactivity descriptors and analysis of the frontier orbitals.

Mononuclear Pseudostannatranes Possessing Unsymmetrical [4.4.3.01,5]Tridecane Cage: Experimental and Theoretical Aspects of Reverse Kocheshkov Reaction in Phenyl Pseudostannatrane.

The synthetic protocols, structural aspects, and spectroscopic aspects of mononuclear pseudostannatranes possessing a [4.4.3.01,5]tridecane cage have been reported. A tripodal ligand N(CH2CH2OH){CH2(2-t-Bu-4-Me-C6H2OH)}2 (H3L) having unsymmetrical arms was reacted with n-butyltrichlorostannane, phenyltrichlorostannane, and tin tetrachloride under different solvent systems to obtain pseudostannatranes (1-3). The reaction of n-butyltrichlorostannane and the ligand in CH3OH/Na/THF yielded an aqua complex of pseudostannatrane [LSnBu(H2O)] (1a), which was crystallized as its acetone solvate (i.e 1a·Me2CO). However, the same reactants yielded methanol complex [LSnBu(CH3OH)] (1b) when the reaction was carried out in the NaOCH3/C2H5OH system. Similarly, the reaction of phenyltrichlorostannane and the ligand under these solvent systems yielded pseudostannatranes, i.e., an aqua complex [LSnPh(H2O)] (2a) and a methanol complex [LSnPh(CH3OH)] (2b) (where 2a was crystallized as 2a·Me2CO). The reaction of tin tetrachloride and the ligand in the Et3N/THF system resulted in the formation of pseudostannatrane [LHSnCl2] (3). A similar product was isolated as its triethylamine solvate (3·NEt3) due to the disproportion reaction when PhSnCl3 was reacted with the ligand in the Et3N/C6H5CH3 system, which demonstrates the first report on the reverse Kocheshkov reaction in pseudostannatranes. The experimental findings on the formation of 3·NEt3 due to the reverse Kocheshkov reaction have been corroborated with 119Sn NMR spectroscopy and density functional calculations that provide insightful information about the underlying details of the reaction route.

Single-Atom Catalysis Using Chromium Embedded in Divacant Graphene for Conversion of Dinitrogen to Ammonia.

Reduction of dinitrogen to ammonia under ambient conditions is a long-standing challenge. The few metal-based catalysts proposed have conspicuous disadvantages such as high cost, high energy consumption, and being hazardous to the environment. Single-atom catalysis has emerged as a new frontier in heterogeneous catalysis and metal atoms atomically dispersed on supports receive more and more attention owing to rapid advances in synthetic methodologies and computational modeling. Herein, we propose metal atoms embedded in divacant graphene as a catalyst for N2 fixation based on density functional calculations. We systematically investigate the potential of using transition metal like Cr, Mn, Fe, Mo and Ru as catalysts and our study reveals that Cr embedded in graphene exhibit good catalytic activity for N2 fixation. The synergy between the metal atoms and graphene surface provides a stable support to the metal center that has a high spin density to promote adsorption of N2 and activation of its N≡N triple bond. Our study deciphers the mechanism of conversion of N2 to ammonia following two possible reaction pathways, distal and enzymatic routes, via sequential protonation and reduction of activated N2 . The study provides a rational framework for conversion of dinitrogen to ammonia using single atom catalyst.

Mechanistic details of amino acid catalyzed two-component Mannich reaction: experimental study backed by density functional calculations.

The role of pH-dependent ionic structures of L-amino acids in catalysis has been investigated for the two-component Mannich reactions between dimethyl malonate (DMM)/ethyl acetoacetate (EAA) and imines. As catalysts, L-amino acids performed well, even better than corresponding base catalysts and provided the ß-amino carbonyl compounds in very high yields. Density functional calculations were used to gain the mechanistic insight of the reaction. High catalytic efficiency of amino acids was attributed to the facile formation of carbanion intermediate through barrierless transition state TS1 (- 19.43 kcal/mol) and then its stabilization owing to carbanion interaction with protonated amino acid.

Correction: Enantioselective synthesis of sulfoxide using an SBA-15 supported vanadia catalyst: a computational elucidation using a QM/MM approach.

Correction for 'Enantioselective synthesis of sulfoxide using an SBA-15 supported vanadia catalyst: a computational elucidation using a QM/MM approach' by Navjot Kaur et al., Phys. Chem. Chem. Phys., 2017, 19, 25059-25070.

Enantioselective synthesis of sulfoxide using an SBA-15 supported vanadia catalyst: a computational elucidation using a QM/MM approach.

Metal catalyzed asymmetric oxidation of prochiral sulfides is one of the prevailing strategies to produce enantiopure sulfoxides. Keeping in view the reported reactivity of peroxo vanadium complexes towards asymmetric oxidation reactions, this study explores the reactivity of vanadia represented as a VO4 cluster with CH3-S-Ph through DFT computations. The mechanism of the oxidation of sulfides to sulfoxides with unsupported VO4 is thoroughly investigated. The chiral centre in the VO4 cluster is introduced by grafting it on an SBA-15 support and two conformers of the supported cluster are thus obtained. The study was extended to locate transition states for the reaction of each conformer with CH3-S-Ph. The large enantiomeric excess obtained from the energy difference of the transition states confirms the formation of enantiopure sulfoxide. Analysis of the computational results provides a rational explanation for the observed enantioselectivity, which is remarkable. The optical stability as well as asymmetry of chiral sulfoxides obtained by the current approach has been further confirmed by locating the planar transition state, through which conversion from one enantiomer to another takes place. The calculations suggest that transition between the two enantiomers of sulfoxide is hampered by sufficiently high inversion barriers.

Theoretical study of adsorption of amino acids on graphene and BN sheet in gas and aqueous phase with empirical DFT dispersion correction.

Understanding interactions of biomolecules with nanomaterials at the molecular level is crucial to design new materials for practical use. In the present study, adsorption of three distinct types of amino acids, namely, valine, arginine and aspartic acid, over the surface of structurally analogous but chemically different graphene and BN nanosheets has been explored within the formalism of DFT. The explicit dispersion correction incorporated in the computational methodology improves the accuracy of the results by accounting for long range van der Waals interactions and is essential for agreement with experimental values. The real biological environment has been mimicked by re-optimizing all the model structures in an aqueous medium. The study provides ample evidence in terms of adsorption energy, solvation energy, separation distance and charge analysis to conclude that both the nano-surfaces adsorb the amino acids with release of energy and there are no bonded interactions between the two. The polarity of the BN nanosheet provides it an edge over the graphene surface to have more affinity towards amino acids.

Spin Inversion Phenomenon and Two-State Reactivity Mechanism for Direct Benzene Hydroxylation by V4O10 Cluster.

The direct and selective introduction of hydroxyl group into aromatic compounds remains one of the challenging problems in oxidation chemistry. Keeping in view the reported reactivity of vanadium oxide in C-H activation of saturated hydrocarbons, the study explores the reactivity of neutral V4O10 cluster with benzene through rigorous computations performed within the formalism of density functional theory. Three possible reaction channels for the reactivity of V4O10 cluster with benzene have been deciphered, and comprehensive understanding of all possible mechanistic pathways has been obtained by analysis of all the intermediates and transition states encountered en route. The study provides promising evidence of direct abstraction of hydrogen by terminal oxygen of the cluster via three-centered transition state. The scan of potential energy surfaces for the reactivity of the cluster in its ground (singlet) and first excited (triplet) spin multiplicity states establishes two-state reactivity mechanisms. The spin crossover point has been identified through geometric and thermodynamic parameters, partial charges, and intrinsic reaction coordinate calculations. The study establishes the efficacy of V4O10 cluster species in direct hydroxylation of benzene to phenol.

Encapsulation of heavy metal ions via adsorption using cellulose/ZnO composite: First principles approach.

The primary goal of the current research is to describe an effective and eco-friendly adsorbent for the removal of aquatic micropollutants. The design of the cellulose-modified zinc oxide (ZnO) nanocomposite was successfully carried out by density functional calculations. The proposed structures of the constituent and composite materials were confirmed using formation energy (Ef), frontier orbitals, band gaps (Egap), density of state (DOS) plots, natural bond orbitals (NBO), and UV-Vis spectral analysis. The cellulose/(ZnO)12 composite was further used for the adsorption of different heavy metal ions such as Hg(II), Pb(II), Cd(II), Ni(II), and As(III) through calculation of electronic and optical properties. The values of the adsorption energy (Eads) show that the As(III) interacted better with the composite in both phases, i.e., gas (-806.98 kcal/mol) and aqueous (-491.66 kcal/mol). The analysis of frontier molecular orbital data exhibited a decrease in the Egap of composite@metal ion complexes. The high negative value of the solvation energies (ΔEsol) indicates the suitability of composite@metal ions in an aqueous environment. The nature of interactions between metal ions and the composite unit is analyzed by noncovalent interactions (NCI) and the quantum theory of atoms in molecules (QTAIM). The theoretical results of the present study show the feasibility of the cellulose/(ZnO)12 composite for the removal of heavy metal ions and provide useful information to experimentalists to treat contaminated water.

Photodegradation of dye using Polythiophene/ZnO nanocomposite: A computational approach.

Incorporating nanostructured photocatalysts in polymers is a strategic way to obtain novel water purification systems. Here, we present density functional theory (DFT) study of Polythiophene/Zinc oxide (PTh/ZnO) nanocomposite with high photocatalytic performance and stability which exhibits superior degradation of alizarine dye under the visible light condition with interaction energy of -149.55 kcal/mol between conducting polymer (PTh) and metal oxide, with PTh sponsoring more number of electrons to the conduction band of ZnO. The electrical and optical properties of optimized geometries of PTh/ZnO nanocomposite were studied by frontier molecular orbital analysis, natural bond orbital (NBO) charge simulation, natural electronic configuration, and UV-vis absorption spectra. The modulation of the energy band gap (∽ 2.60 eV) and exciton binding energy (∽ 0.36 eV) causes visible light absorption and hence enhances the photodegradation activity of PTh/ZnO. NBO analysis evidences the electron accepting behavior of ZnO in the composites as it withdraws electron cloud density of about 0.14e from the polymer unit.

Structural evolution and stability of hydrogenated Li(n) (n = 1-30) clusters: a density functional study.

The structure and electronic and optical properties of hydrogenated lithium clusters Li(n)H(m) (n = 1-30, m ≤ n) have been investigated by density functional theory (DFT). The structural optimizations are performed with the Becke 3 Lee-Yang-Parr (B3LYP) exchange-correlation functional with 6-311G++(d, p) basis set. The reliability of the method employed has been established by excellent agreement with computational and experimental data, wherever available. The turn over from two- to three-dimensional geometry in Li(n)H(m) clusters is found to occur at size n = 4 and m = 3. Interestingly, a rock-salt-like face-centered cubic structure is seen in Li(13)H(14). The sequential addition of hydrogen to small-sized Li clusters predicted regions of regular lattice in saturated hydrogenated clusters. This led us to focus on large-sized saturated clusters rather than to increase the number of hydrogen atoms monotonically. The lattice constants of Li(9)H(9), Li(18)H(18), Li(20)H(20), and Li(30)H(30) calculated at their optimized geometry are found to gradually approach the corresponding bulk values of 4.083. The sequential addition of hydrogen stabilizes the cluster, irrespective of the cluster size. A significant increase in stability is seen in the case of completely hydrogenated clusters, i.e., when the number of hydrogen atoms equals Li atoms. The enhanced stability has been interpreted in terms of various electronic and optical properties like adiabatic and vertical ionization potential, HOMO-LUMO gap, and polarizability.

Qualitative as well as quantitative analysis of interactions present in chlorine and bromine substituted aromatic organic crystals: A DFT linked Crystal Explorer study.

The effect of noncovalent interactions in shaping a crystal structure is explored qualitatively as well as quantitatively in a DFT linked Crystal Explorer (CE) study of nine different Chlorine and Bromine substituted benzene derivatives. The qualitative approach to analyze interactions is based on Hirshfeld surface that locates electronic charge distribution on the surface, quantitative estimation is obtained by linking DFT computations withCE.In the halogen substituted benzene derivatives considered here, in addition to conventional hydrogen and halogen bonding other interactions such as those between Chlorine-Hydrogen, Bromine-Hydrogen, Bromine-Oxygen have been deciphered. The molecular crystal structure of a variety of halogen substituted aromatic molecules has been rationalized and attributed to specific interactions.

Conceptual DFT and TDDFT study on electronic structure and reactivity of pure and sulfur doped (CrO3)n (n = 1-10) clusters.

Different isomers of (CrO3)n (n = 1-10) cluster units have been investigated using Density functional approach. Their stability and reactivity has been analyzed by plotting chemical potential and HOMO-LUMO gap as a function of cluster size. The CrO3, (CrO3)6 and (CrO3)9 are identified as the most reactive species. Reactivity of each atomic site in the cluster has been interpreted using local reactivity descriptors called Fukui Function plots. The clusters have been doped with sulfur by adding it as substitutional impurity, effect of sulfur doping has been understood by analyzing excitation energies and absorption wavelengths using time dependent-DFT(TDDFT) at CAM-B3LYP level of theory.

Understanding structure-activity relation in VxOy clusters of varied stoichiometry and sizes through conceptual density functional approach.

Computations have been performed on VxOy clusters (with x = 1-8, y = 1-21) to explore their structure, stability, and reactivity based on local and global reactivity descriptors defined within the formalism of density functional theory (DFT). The vertical and adiabatic ionization energies and electron affinities are in accordance with Franck-Condon principle and suggest that the VxOy clusters are more likely to be electron acceptors than donors. The structure and reactivity of VxOy clusters delicately depend on their oxygen content and environment. Distinct active sites have been identified for each cluster species on the basis of coordination, symmetry, and charge distribution. The propensity of all the reactive sites towards an approaching electrophile and/or nucleophile has been studied using local reactivity descriptor. In oxygen-poor clusters, the vanadium atoms are more prone to nucleophilic attack. With an increase in oxygen concentration, the coordination number of vanadium increases and reaches four-fold, the site for nucleophilic attack shifts to terminal oxygens. We conclude that of all the stoichiometries, the stable VxOy clusters have the (VO3)a(V2O5)b formula unit. The localization of positive charge density in cubic cage structure of V8O20 successfully traps halide ions (F-, Cl-, and Br-). In view of increasing use of metal oxide clusters in heterogeneous catalysis, the understanding of structure-activity relationship in vanadium oxides' clusters provided in the current study is highly desirable.

Nucleotide conjugated (ZnO)3 cluster: Interaction and optical characteristics using TDDFT.

Binding of four DNA nucleotide units with (ZnO)3 cluster in an aqueous phase has been investigated using density functional theory (DFT) and time dependent-density functional theory (TDDFT) method and the stability order for (ZnO)3-nucleobases/sugar/phosphate systems is predicted as phosphate > C > A > S > T ∼ G. The order of binding energy for (ZnO)3-nucleotide hybrid systems is observed to be (ZnO)3 + nuc-C ˃ (ZnO)3 + nuc-A ˃ (ZnO)3 + nuc-G ˃ (ZnO)3 + nuc-T. The binding of nucleotide units with the cluster has been explained on the basis of molecular electrostatic potential (MEP) plots, hydrogen bonding, glycosidic torsion angles, density of state (DOS) plots. The photophysical properties of (ZnO)3-nucleotide complexes have been studied using TDDFT approach. Among all (ZnO)3-nucleotide complexes, the absorption spectra of (ZnO)3 + nuc-A and (ZnO)3 + nuc-C complexes are seen to undergo red shift with respect to their bare nucleotide units that would be useful in the optical sensing of the respective nucleotides of DNA. It is interesting to note that binding of the nucleotide unit with the cluster makes it fluorescent, the study reports the fluorescence activity of (ZnO)3 + nuc-T complex.