The curious case of co-planarity in di-nuclear triel complexes: a density functional investigation.

Density functional investigation of intramolecular triel (Tr) bonding present in di-nuclear aryl complexes of group 13 elements having general formula [(Tr)Me(2,6-(X)CHO)] (Tr = B, Al, Ga, In & Tl and X = OMe, OEt, OH, OPh, NH, SH, Cl, F) has been performed. Conclusive evidence of the concurrent two σ-hole interaction has been provided by analysis of the Tr bond length, interaction energy (Δ), second order perturbation energy (), charge transfer (Δ), quantum theory of atom in molecules (QTAIM) and noncovalent interaction (NCI) plots for 12 complexes. The Tr bond length in the optimized geometry varies from 2.

Engineering highly efficient porphyrin sensitizers through metal, ligand and bridge modification: a DFT study.

This work presents a systematic investigation of porphyrin sensitizers for application in dye-sensitized solar cells (DSSCs). Density functional theory calculations, including both static and time-dependent methods, were employed to evaluate a series of candidate dyes for their potential to achieve high power conversion efficiency. The well-established SM315 dye, known for its record-breaking PCE of 13%, was adopted as a reference point.

First-Principles Characterization of Noncovalent Interactions in the Enantioselective Oxetane Ring Opening via SPHENOL-Based Chiral Phosphoric Acid Catalyst.

The asymmetric ring-opening reaction of 3,3-substituted oxetanes catalyzed by chiral phosphoric acid (CPA) derived from a newly developed SPHENOL (2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diol) framework was investigated by performing density functional calculations. The plausible transition states were traced by considering the oxetane activation mode. The energy profiles obtained for various substrates provide a rational understanding of the reaction at the atomic level.

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 λ)ρ provide insights into the noncovalent interactions between the composite units.

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, NO, 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 (Δ), second-order perturbation energy (), charge transfer (Δ), 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.

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 (E), frontier orbitals, band gaps (E), density of state (DOS) plots, natural bond orbitals (NBO), and UV-Vis spectral analysis.

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 = 2-100 atoms are reported. For = 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 = 2-11 were subsequently studied further through density-functional-theory calculations.

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.

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 SiX H -H O and 16 ternary complexes, of general formula NaX-SiX H -H 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 SiX H -H O gets strengthened up to 49 %, owing to cooperativity effect exerted by hydrogen bonding between X and H in the ternary complex NaX-SiX H -H O.

Kinetics and Thermodynamics of CO Oxidation by (TiO).

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.

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.

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

Different isomers of (CrO) (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 CrO, (CrO) and (CrO) are identified as the most reactive species.

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.

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 β-amino carbonyl compounds in very high yields. Density functional calculations were used to gain the mechanistic insight of the reaction.

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

Computations have been performed on VO 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 VO clusters are more likely to be electron acceptors than donors. The structure and reactivity of VO clusters delicately depend on their oxygen content and environment.

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.

A QM/MM study on ethene and benzene oxidation using silica-supported chromium trioxide.

Oxidation of ethene and benzene by chromium oxide (CrO) supported on silica (SiO) was investigated by employing hybrid quantum mechanics/molecular mechanics (QM/MM) model calculations. Various mechanistic possibilities, such as C-H or C=C bond activation of hydrocarbons, were investigated in detail for the reaction of ethene and benzene with CrO grafted on a silica surface. While activation of the C-H bond leads to the formation of alcohol, epoxide is obtained via C=C bond activation.

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

Binding of four DNA nucleotide units with (ZnO) 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)-nucleobases/sugar/phosphate systems is predicted as phosphate > C > A > S > T ∼ G. The order of binding energy for (ZnO)-nucleotide hybrid systems is observed to be (ZnO) + nuc-C ˃ (ZnO) + nuc-A ˃ (ZnO) + nuc-G ˃ (ZnO) + 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.

Functionalized magnetic nanomaterials for rapid and effective adsorptive removal of fluoroquinolones: Comprehensive experimental cum computational investigations.

Alarming growth of pharmaceutical residues in aquatic environment has elevated concerns about their potential impact on human health. Taking cognizance of this, the present study is focussed on the coating of cobalt ferrite nanoparticles with different functionalities and to use them as adsorbents for pharmaceutical waste. The thickness of the coating was analysed using Small angle X-ray scattering technique.

Correction to: Removal of fluoroquinolone from aqueous solution using graphene oxide: experimental and computational elucidation.

Unfortunately, the original version of this article contains a mistake. The figures no. 10, 11, 12 and 13 in the original version of the article should be replaced by the figures shown in this paper.

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.

Removal of fluoroquinolone from aqueous solution using graphene oxide: experimental and computational elucidation.

The environmental risks of antibiotics have attracted increasing research attention due to their prevalence and persistence in the aquatic environment. In this study, oxygen functionalized graphene, namely, graphene oxide (GO), was synthesized by modified Hummer's and Offeman's method and used as potential effective absorbent for the removal of fluoroquinolones (FQs), i.e.

Dispersion corrected density functional study of CO oxidation on pristine/functionalized/doped graphene surfaces in aqueous phase.

The catalytic oxidation of CO by molecular oxygen (O) over graphene, epoxy functionalized graphene and sulphur doped graphene surface is investigated theoretically by employing dispersion corrected Density Functional Theory. The adsorption of O and CO molecules over the pristine, functionalized and doped graphene surface has been compared. The channel for oxidation of CO to CO is elucidated in detail in the presence of aqueous solvent.

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 VO cluster with CH-S-Ph through DFT computations. The mechanism of the oxidation of sulfides to sulfoxides with unsupported VO is thoroughly investigated.