Assessing Computational Methods to Calculate the Binding Energies of Dimers of Five-Membered Heterocyclic Molecules.

Computational electronic structure methods, including ab initio and density functional theory (DFT), have been assessed in calculating the binding energies of 14 five-membered heterocyclic dimers. The configurations were generated using classical molecular dynamics before optimization at the MP2/aug-cc-pVTZ. Benchmark binding energies are calculated at the CCSD(T)/CBS level of theory.

Unexpected XPS Binding Energy Observations Further Highlighted by DFT Calculations of Ruthenocene-Containing [Ir(ppy)(RCOCHCORc)] Complexes: Cytotoxicity and Crystal Structure of [Ir(ppy)(FcCOCHCORc)].

The series of iridium(III) complexes, [Ir(ppy)(RCOCHCOR')], with R = CH and R' = CH (), Rc (), and Fc (), as well as R = Rc and R' = Rc () or Fc (), and R = R' = Fc (), ppy = 2-phenylpyridinyl, Fc = Fe(η-CH)(η-CH), and Rc = Ru(η-CH)(η-CH), has been investigated by single-crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS) supplemented by DFT calculations. Here, in the range of 3.74 ≤ Σχ ≤ 4.

Synthesis, Electrochemistry and Density Functional Theory of Osmium(II) Containing Different 2,2':6',2″-Terpyridines.

In coordination chemistry, 2,2':6',2″-terpyridine is a versatile and extensively studied tridentate ligand. Terpyridine forms stable complexes with a variety of metal ions through coordination sites provided by the three nitrogen atoms in its pyridine rings. This paper presents an electrochemical study on various bis(terpyridine)osmium(II) complexes, addressing the absence of a systematic investigation into their redox behavior.

Effect of physicochemical parameters on the occurrence of per- and polyfluoroalkyl substances (PFAS) in aquatic environment.

Perfluoroalkyl substances (PFAS) and their distribution in aquatic environments have been studied extensively, but more information is needed to link these occurrences to their physicochemical characteristics. Understanding how these parameters influence PFAS can help predict their fate, mobility, and occurrences in water. This study reviewed the influence of physicochemical parameters on the occurrences of PFAS in aquatic environment using the relevant keywords to retrieve articles from databases spanning mostly between 2017 and 2024.

Clusters of solvated ferrous ion in water-ammonia mixture: Structures and noncovalent interactions.

The behavior of metal ions is commonly studied in pure solvent although, in our daily life, these metals are involved in mixtures of solvents. In the present study, we investigated structures, relative stabilities and temperature dependance of solvated ferrous ion in water-ammonia mixture solvent at 0K and at various temperatures ranging from 25K to 400K. All the calculations are performed at the MN15 level of theory associated with the aug-cc-pVDZ basis set.

Gold Tripyrrindione: Redox Chemistry and Reactivity with Dichloromethane.

The identification of ligands that stabilize Au(III) centers has led to the isolation of complexes for applications in catalysis, gold-based therapeutics, and functional materials. Herein, we report the coordination of gold by tripyrrin-1,14-dione, a linear tripyrrole with the scaffold of naturally occurring metabolites of porphyrin-based protein cofactors (e.g.

Neutron activation of stable isotopes in soil and groundwater from a radionuclide production facility, South Africa.

The neutron activation of stable isotopes in environmental matrices, such as soil and groundwater, is a critical aspect of assessing the impact of radionuclide production facilities on the surrounding ecosystem. The envisioned Low-Energy Radioactive Ion Beams (LERIB) facility at the iThemba LABS, South Africa is anticipated to generate significant sources of ionising radiation. The study investigated the possible repercussions of neutron irradiation stemming from the facility, focusing on the activation of stable isotopic compositions in the environment.

Scientometric trends and knowledge maps of global polychlorinated naphthalenes research over the past four decades.

Polychlorinated naphthalenes (PCNs) were included in the banned list of the Stockholm Convention due to their potential to provoke a wide range of adverse effects on living organisms and the environment. Many reviews have been written to clarify the state of knowledge and identify the research needs of this pollutant class. However, studies have yet to analyse the scientometric complexities of PCN literature.

Theoretical Photoelectron Spectroscopy of Metal-Metal Quintuple Bonds: Relativity-Driven Reordering of Frontier Orbitals.

A recent reinvestigation of the gas-phase photoelectron spectra of Group 6 metal-metal quadruple-bonded complexes with scalar-relativistic DFT calculations showed that common exchange-correlation functionals reproduce the lowest ionization potentials in a semiquantitative manner. The finding encouraged us to undertake a DFT study of metal-metal quintuple bonds in a set of bisamidinato complexes with the formula M [HC(NR)] (M = Cr, Mo, W; R = H, Ph, 2,6-PrCH) and idealized symmetry. Scalar-relativistic OLYP/STO-TZ2P calculations indicated significant shifts in valence orbital energies among the three metals, which translate to lower first ionization potentials, higher electron affinities, and lower HOMO-LUMO gaps for the W complexes relative to their Cr and Mo counterparts.

Experimental and theoretically calculated structural data of different iron(II)-terpyridine complexes - validation of theoretical method.

Experimental structural data for bis(terpyridine)iron(II) and a series of related iron(II) complexes, featuring either substituted terpyridine or tris-azinyl analogues of terpyridine, are presented and analyzed in terms of the Mean Absolute Deviation (MAD) from the average experimental data for each specific complex. The experimental structural data are then juxtaposed with density functional theory (DFT) calculated data obtained using various combinations of DFT functionals and basis sets, with and without the inclusion of Grimme D3 empirical dispersion correction. These diverse computational approaches yield optimized geometries that are subsequently compared against the available experimental structural data to assess their accuracy.

Theoretical study of the photoisomerization of 1,2-bispyrazinyl-ethylene and the halogen ion salts of 1-Pyrazinyl-2-(4'-methylpyrazinyl)ethylene.

Context: It has been reported that photoexcitation of azastilbene compounds like E-1,2-bispyrazinyl-ethylene (bpe) can undergo E → Z photoisomerization of its quaternary salts via the excited triplet state. However, experimentally it is possible to get low fluorescence and photoisomerisation quantum yields in a state with higher internal conversion than intersystem crossing. We modelled bpe and its methylated derivative (bpeMe), as well as its quaternary halogen salts (bpeMeX with X = F, Cl, Br and I) to study levels of fluorescence, phosphorescence and excited state potential energy surfaces (PES).

Theoretical Photoelectron Spectroscopy of Quadruple-Bonded Dimolybdenum(II,II) and Ditungsten(II,II) Paddlewheel Complexes: Performance of Common Density Functional Theory Methods.

We have revisited the gas-phase photoelectron spectra of quadruple-bonded dimolybdenum(II,II) and ditungsten(II,II) paddlewheel complexes with modern density functional theory methods and obtained valuable calibration of four well-known exchange-correlation functionals, namely, BP86, OLYP, B3LYP*, and B3LYP. All four functionals were found to perform comparably, with discrepancies between calculated and experimental ionization potentials ranging from <0.1 to ∼0.

DFT study of the spectroscopic behaviour of different iron(II)-terpyridine derivatives with application in DSSCs.

Through a comprehensive computational analysis utilizing Density Functional Theory (DFT), we clarify the electronic structure and spectroscopic properties of modified iron(II)-terpyridine derivatives, with the aim of enhancing the efficiency of Dye-Sensitized Solar Cells (DSSCs). We optimized a series of nineteen iron(II)-terpyridine derivatives and related compounds in acetonitrile (MeCN) as the solvent using TDDFT, evaluating their potential as dyes for DSSCs. From the conducted computations on the optimized geometries of the nineteen [Fe(L)] complexes, containing substituted terpyridine and related ligands L-L, we determined the wavelengths (λ in nm), transition energy (E in eV), oscillator strength (f), type of transitions, excited state lifetime (τ), light harvesting efficiency (LHE), frontier orbital character and their energies (E/E), natural transition orbitals (NTOs), injection driving force of a dye (ΔG), and regeneration driving force of a dye (ΔG).

Quantum cluster equilibrium theory applied to liquid ammonia.

Through this paper, the authors propose using the quantum cluster equilibrium (QCE) theory to reinvestigate ammonia clusters in the liquid phase. The ammonia clusters from size monomer to hexadecamer were considered to simulate the liquid ammonia in this approach. The clusterset used to model the liquid ammonia is an ensemble of different structures of ammonia clusters.

Solvation energies of the ferrous ion in water and in ammonia at various temperatures.

Context: The solvation of metal ions is crucial to understanding relevant properties in physics, chemistry, or biology. Therefore, we present solvation enthalpies and solvation free energies of the ferrous ion in water and ammonia. Our results agree well with the experimental reports for the hydration free energy and hydration enthalpy.

Hydration of [Formula: see text]aminobenzoic acid: structures and non-covalent bondings of aminobenzoic acid-water clusters.

Context: Micro-hydration of the aminobenzoic acid is essential to understand its interaction with surrounding water molecules. Understanding the micro-hydration of the aminobenzoic acid is also essential to study its remediation from wastewater. Therefore, we explored the potential energy surfaces (PESs) of the para-aminobenzoic acid-water clusters, ABW[Formula: see text], [Formula: see text], to study the microsolvation of the aminobenzoic acid in water.

Effect of density functional approximations on the calculated Jahn-Teller distortion in bis(terpyridine)manganese(III) and related compounds.

Context: Bis(terpyridine)manganese(III) exhibits Jahn-Teller distortion due to the inequivalent occupation of the degenerate e orbitals of this high-spin d pseudo octahedral complex. Due to the spatially constrained nature of the terpyridine ligand, the central Mn-N bonds will always be shorter than the Mn-N terminal bonds, making it more difficult to distinguish between compression and elongation Jahn-Teller structures for bis(terpyridine)manganese(III). Density functional theory (DFT) calculations were utilized as a tool to evaluate the type of Jahn-Teller distortion in the high-spin d bis(terpyridine)manganese(III).

Isolation, characterization and modulatory potentials of -stigmasterol, ergosterol and xylopic acid from on mitochondrial permeability transition pore .

Objective: Secondary metabolites and polyphenolic compounds from medicinal plants have been demonstrated to have multiple biological functions with promising research and development prospects. This study examined the effect of -stigmasterol (with ergosterol) and xylopic acid isolated from on liver mitochondrial permeability transition pore (mPTP).

Methods: The compounds were isolated by vacuum liquid chromatography.

Adsorption of some cationic dyes onto two models of graphene oxide.

Context: The search for highly efficient adsorbent materials remains a significant requirement in the field of adsorption for wastewater treatment. Computational study can highly contribute to the identification of efficient material. In this work, we propose a computational approach to study the adsorption of four cationic basic dyes, basic blue 26 (BB26), basic green 1 (BG1), basic yellow 2 (BY2), and basic red 1 (BR1), onto two models of graphene oxide as adsorbents.

Structures of DMSO clusters and quantum cluster equilibrium (QCE).

Dimethylsulfoxide (DMSO) clusters are crucial for understanding processes in liquid DMSO. Despite its importance, DMSO clusters have received negligible attention due to the complexity of their potential energy surfaces (PESs). In this work, we explored the PESs of the DMSO clusters from dimer to decamer, starting with classical molecular dynamics, followed by full optimizations at the PW6B95-D3/def2-TZVP level of theory.

Free-Base Corrole Anion.

Free-base corroles have long been known to be acidic, readily undergoing deprotonation by mild bases and in polar solvents. The conjugate base, however, has not been structurally characterized until now. Presented here is a first crystal structure of a free-base corrole anion, derived from tris(-cyanophenyl)corrole, as the tetrabuylammonium salt.