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Microwave assisted condensation of 3-acetyl-2,5-dimethylthiophene (1) and 9-ethyl-9H-carbazole-3-carbaldehyde (2) gave 1-(2,5-Dimethylthiophen-3-yl)-3-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one (chalcone) (1.1) which was cyclized to pyrazoline (1.2, 1.3), and pyrimidine (1.4, 1.5) derivatives. All the synthesized compounds were subjected to antibacterial activity evaluation using two Gram + ve and two Gram-ve bacterial strains and were tested for any possible toxic effect to the mammalian cells. Density functional theory was used to understand the electronic structure of the studied molecules. All the molecules were modeled and optimized using B3LYP/6-311 + G** level of theory. The relationship between activities and Frontier Molecular orbital (HOMO and LUMO orbitals) of the compounds is also discussed. Docking studies were also performed. The observed results revealed that the pyrazoline skeleton is a promising lead structure, which displays higher in vitro antibacterial efficacy, probably by interacting and inhibiting the glucosamine-6-phosphate synthetase enzyme (GlmS). Theoretical calculations are in good agreement with the in vitro and in silico findings.

1,1′-Bis (1-methyl pyridinium-2-yl)-4,4′-dipyridinium dichloride di-iodide (TPy) and 1,1′-dimethyl-4,4′-dipyridinium di-iodide (DPy) have been synthesized and used as corrosion inhibitors for ferritic type 430 stainless steel in 0.5 M H 2 SO 4 solution. Polarization, weight loss and scanning electron microscopic measurements confirm the inhibitive action of these compounds and the increase in inhibition efficiency with an increase in concentration and temperature. The compounds enhance the passivation of the steel by increasing suppression of the critical current. The quantum chemical calculations explain the good adsorption of these compounds on the steel surface and the greater inhibition efficiency for TPy compared with that of DPy inhibitor.

Detailed DFT computations and classical trajectory dynamics simulations have been carried out to establish the origin of the extra stability of alloxan. The effect of solvent, basis set and DFT methods have been examined. Two non-covalent intermolecular dimers of alloxan, namely the H- bonded and the dipolar dimers have been investigated to establish their relative stability. Quantum theory of atom-in-molecule and NBO analysis has been performed.

The gas phase conformational and nonlinear optical properties of cis-N-phenylbenzohydroxamic acid (cis-NPBHA) keto and enol forms were studied applying traditional hybrid and long-range-corrected Density Functional Theory (DFT) and time-dependent density functional (TD-DFT) methods. The calculated geometrical parameters for the two isomers agreed satisfactorily with literature ones. The keto form was predicted to be more stable than the enol counterpart by 10.70–12.60 kcal/mol, and the Gibb’s free energies for the conversion: enol⇌keto were found to be 11.14 kcal/mol (B3LYP/6-311+G**), 12.53 kcal/mol (CAM-B3LYP/6-311+G**) and 13.28 kcal/mol (ωB97XD/6-311+G**). All the selected functionals have computed larger total hyperpolarizabilities for the enol tautomer compared to those of the keto rival. The traditional hybrid functional yielded higher total hyperpolarizabilities than those of the long-range-corrected ones. The total hyperpolarizabilities were nicely correlated with HOMO–LUMO energy gaps and absorption maxima. The support of these molecular properties by natural bond orbital (NBO) calculations was evaluated and discussed.

The transition structures and the activation energies for the possible thermal elimination of H2O, HF and HCl from ethane-1,2-diol, 2-fluoroethanol and 2-chloroethanol respectively, were investigated. The relative stabilities and associated barrier heights of syn and anti vinyl alcohol isomers and their acetaldehyde tautomer were estimated. HF, DFT/B3LYP and MP2 methods at 3-21G, 6-31+G(d), 6-311++G(d,p) and aug-cc-pvdz basis sets were applied to identify the stationary points of the studied systems. The optimized geometries and electronic energies of reactants, transition states and products were analyzed. The dependence of these properties upon the theoretical level was discussed. A concerted proton release and a hydroxide or halide ion expulsion mechanism was proposed to account for the thermal rearrangement of reactants to products. A thorough understanding of syn vinyl alcohol preference is provided by performing natural bond orbital (NBO) analysis. The oxygen atom lone pair (LP) and periplanar hyper...

The present work attempts to assess and evaluate the performance of some new DFT methods in describing van der Waals (vdW) complexes that are characterized by the dominance of pure dispersion interactions. To achieve this goal, Argon dimers (Ar2) and trimers (Ar3) were investigated. As a reference calculation, the correlation interaction energy have been computed at the CCSD(T) level using the aug-correlated family of basis sets pVXZ (where X=2,3,4). Extrapolation to the CBS limit has been carried out and the behavior of the potential energy function has been analyzed and discussed. Correlation interaction energy has been computed at the MP2 and MP4 levels and compared to those calculated at the CCSD(T) method. Five new correlated DFT functionals, namely M06 and its long rang extension M06L, the B97-2 and its modified version B97-D which was deviseded for the dispersion interaction, and the PBEPBE and its correlated extension PBE0 methods have been used to compute the interaction energy in Ar2 and Ar3. The present work results indicate clearly that M06 and M06L did not only overestimate the equilibrium distance and depth but they also showed fluctuations in the potential energy curve near the minimum and along the dissociative arm. The B97-D and the PBE0 methods are much more reliable. However, these two later methods showed convergence problems when used to treat Ar3+; in addition to being extremely fast when compared to the CCSD(T) method extremely fast as compared to the CCSD(T). These features make them good candidate for investigating large vdW clusters. The BSSE has been estimated, analyzed and discussed. The relative stabilities of the excited states of Ar2 and Ar3 clusters together with those of the ionic species (Ar2+ and Ar3+)have been computed and analyzed.

The electronic structure, the origin of the extraordinary stability and the reaction mechanisms of the decomposition reaction of the three-membered ring cyclopropenone (IO), its phenyl derivative (IIO) and its sulfur analogues (IS and IIS) have been investigated at the B3LYP/6-311+G** level of theory. All critical points on the reaction surface, reactants, transition states and intermediates were determined. Reaction rate constants and half-lives have been computed. Natural bond orbital (NBO) analysis has been used to investigate the type and extent of interaction in the studied species. Results indicate that the decomposition reaction occurs via a stepwise mechanism, with the formation of a short-lived intermediate. The characters of the intermediates for the decomposition of IIO and IIS are different. In case of IIO decomposition, the intermediate structure is of prevailing zwitterionic character, whereas that for the decomposition of IIS is of prevailing carbene character. Solvent effects are computed, analyzed and discussed.

In this study, nano-sized powder of cerium (IV) oxide was prepared through the thermal decomposition reaction of Ce 2 (C 2 O 4 ) 3 ⋅ 10H 2 O. The thermal decomposition course was followed using differential thermal analysis–thermogravimetry (DTA–TG) techniques. Kinetic analysis of the dynamic TG curves was carried out, to obtain kinetic parameters for the decomposition of cerium oxalate into ceria, using three integral methods: Ozawa, Coats–Redfern, and Diefallah composite method. The produced ceria as well as calcined samples at different temperatures up to 950 °C were characterized using X-ray diffraction (XRD), Fourier transform infra-red (FT-IR) and transmission electron microscopy (TEM) techniques. The change in the structural and morphological properties with heat treatment was studied. Surface area measurement was carried out for the calcined samples at different temperatures to characterize the surface properties of the investigated samples. Electrical property as a function of temperature and frequency was measured to determine the conductivity as well as the conduction activation energy and to describe the conduction mechanism. The density functional theory (DFT) was used to describe the chemical bonding characteristics of the prepared compound. The obtained results were discussed to show the effect of heat treatment on the structural, morphological, superficial and electrical properties of ceria.

The gas-phase decomposition mechanism of the photochemical and thermal reaction of cyclopropenone leading to carbon monoxide and acetylene has been investigated theoretically. We employed the B3LYP, MP2, and CASSCF methods with the 6-311 + G** basis set to determine the pathways and the potential energy surface (PES) of this reaction. PES minima were characterized by the absence of any imaginary frequencies and compared with the transition states that contained single imaginary frequencies. The intrinsic reaction coordinate (IRC) method was used to find the minimum energy paths in which reactants and products were connected to the transition states. Activation barrier, thermodynamic, and IRC analyses were performed using the above three methods. Our computations indicated that the decomposition of cyclopropenone proceeds through a stepwise mechanism containing two transition states (TS1 and TS2) and an intermediate. The results show that TS1, the critical transition state, determines the rate of the cyclo...

The tautomerisation reaction of 1,2,3-triazole and some of its derivatives has been studied and the transition states were located. The analysis of results indicates that 2H-triazole is more stable than the 1H-tautomer in all studied compounds in gas phase and in solution. The proton detachment energies and the geometries of the compounds studied were analysed using density functional theory (DFT) and Hartree–Fock (HF) methods in gas phase and solution. Deprotonation takes place in all cases studied by the detachment of N–H proton. The solvent effect on the stability the tautomeric and anion forms of studied compounds has been examined using B3LYP/6-31G* level of theory by applying the polarisable continuum model.

A density functional theory study of the behavior of hemispherands toward alkali metal ions (Li+, Na+, and K+) is performed. The effect of the replacement of the rigid anisyl group(s) by the mobile ether group(s) on the binding energy of hemispherands with alkali metal ions is investigated. The results indicated that the binding energies are inversely proportional to the ionic radius of the cations. Moreover, increasing the flexibility of the ligand results in decreasing the binding toward small ions. The structures of the hosts and the guests are correlated to the binding energies, and the correlations are interpreted in terms of the principle of preorganization. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

N-Bromosuccinimide (NBS) is a brominating and oxidizing agent that is used as a source of bromine. The proton affinities, the tautomeric forms and N Br bond dissociation of NBS have been computed using the B3LYP functional as implemented in the density functional approach. The electronic structures of all possible tautomeric forms of NBS have been thoroughly investigated. The keto form of NBS has been shown to be more stable than any other tautomeric forms. The geometries and relative energies for various stationary structures were determined. The results indicate clearly that O-site protonation is strongly favored over N-site protonation for the studied compound in case of mono- and di-protonation. The bond dissociation energies (BDEs), involving the formation of the bromine radical, cation, and anion, of the N Br bond have been investigated. The N Br BDE of the Br radical formation is lower than that of the Br anion or cation. These conclusions are in good agreement with the experimental results.

The oxidation of [CrIII(HNTA)(Hist)(H2O)]− and [CrIII(HNTA)(Asp)(H2O)]− (NTA = nitrilotriacetate, Hist = l-histidinate and Asp = dl-aspartate) by periodate in aqueous medium has been studied spectrophotometrically between 15.0 and 35.0 °C under pseudo-first-order conditions, [IO4 −] ≫ [complex]. The rate increases over the pH range 3.40–4.45 in both cases, but the two complexes give different rate laws. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4 − to chromium(III). A common mechanism for the oxidation of some chromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between ΔH* and ΔS* values for these reactions.

Spherands are highly preorganized hosts composed of methoxy 1, fluoro 2, and cyano 3 benzene units attached to one another at their 2,6-positions. Density functional theory calculations were used to investigate the complexation between these spherands and alkali metal ions (Li ! , Na ! , and K ! ) to understand the intrinsic factors affecting cation complexation. A comparison of binding energies for these spherands shows that, this order O-Me " " F " " CN. Although anisyl units are basically poor ligands for metal ions, the rigid placements of their oxygen during synthesis rather than during complexation are undoubtedly responsible for the enhanced binding and selectivity of the spherand. The ion-dipolar moiety interactions are found to be the main factors affecting the preference of external binding in the CN-spherands. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 1515-1521, 2009

The optimized geometries and energies of the four cyclic structures of the orotic acid–water complex are computed using density functional theory (B3LYP) combined with the 6-31++G(d,p) basis set. In the three most stable cyclic structures, the water molecule accepts the NH proton and donates a proton to the carbonyl oxygen atoms. Less stable cyclic complexes involving the C5H bond also formed. The proton affinity of the oxygen atoms and the deprotonation enthalpy of the NH bonds of orotic acid are computed at the same level and compared with reported data on uracil and thymine. The most stable cyclic complex is formed at the oxygen lone pair characterized by the lowest basicity and at the NH bond characterized by the highest acidity. Although intrinsic acidities are lower in orotic acid than in uracil and thymine, the binding energies with one water molecule do not differ markedly for uracil and orotic acid. Substituent of carboxylic group at the 6-position, however do not seem to have much effect on the proton affinities and the deprotonation enthalpy of uracil.

Fluorospherands (F-spherands) are highly preorganized hosts composed of fluorobenzene or 4-methylfluorobenzene units attached to one another at their 2,6-positions. To understand the intrinsic factors affecting cation complexation, we investigated the complexation behavior between F-spherands and cations using density functional theory (DFT) at the level of B3LYP/6-31G**. The F6-spherand (C6H3F)6, (1) has a highly preorganized spherical cavity, which can encapsulate Li and Na . Its cavity is not big enough for K and NH4 , which prefer external binding. Plausible conformations were studied for F8-spherand (C6H3F)8. Conformer of D2d symmetry (2b) is more stable than that of D4d (2a), in agreement with NMR experiments. The cavity size of F8-spherand is big enough to encapsulate all cations studied. However, the cavity size of 2b is smaller than that of 2a, which resulted in the guest selectivity. Upon complexation, 2b conformation is more stable for Li and Na , while 2a conformation is preferred for larger cations such as K and NH4 . Thus, the ab initio calculations over these highly preorganized fluorospherands give important insights into their host–guest chemistry. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem 107: 930–936, 2007

Ab initio molecular orbital computation has been performed to study the electronic structure, substituent and solvent effects on the singlet–triplet gaps of a series of nitrenium ions. DFT calculations at the B3LYP/6-311++G** level of theory predict that, the nitrenium ions derived from the metabolism of the antitumor 2-(4-aminophenyl)benzothiazoles exist in the ground singlet state. The preferential stabilization of the singlet state relative to the triplet is due to the transfer of charge density from the phenyl ring to formally electron deficient nitrogen atom. Calculations in solution were carried out using the PCM model. Solvent–solute interaction energies were estimated and reflect a considerable net stabilization of the triplet species at the PCM model. Fourier transform analysis of the internal rotation potential energy function, around the exocyclic bond (C 4 –N), has been performed for niternium ions studied. The magnitudes and origin of the potential energy barriers have been discussed.

The ground-state equilibrium geometries of benzothiazole, benzoxazole, and benzimidazole were optimized at the density functional theory (DFT)/6-31G** level of theory. Proton affinities on each of the possible sites in the studied series of compounds have been calculated at the DFT/6-31G**/6-311G** level. The results indicate clearly that N-site protonation is strongly favored over X-site protonation (X NH, O, S) for the series studied. Correlation of the computed proton affinities to the energy (EHOMO) of the highest occupied MO in the gas phase and in solution has been explored and discussed. A comprehensive investigation of the effect of solvent on the process of protonation of the studied compounds has been performed. Different dielectric continuum models (i.e., Onsager, PCM, and IPCM) have been tested; their performance and range of applicability are reported and discussed. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem 103: 332-343, 2005

The molecular geometry of orotic acid was fully optimized using the gradient minimization technique. The computed geometrical parameters at the B3LYP/6-311G** level correspond well to those determined experimentally by X-ray diffraction. The relative stability of both the syn and anti conformations was investigated at the B3LYP/6-311G** level, where the syn-form was shown to be slightly more stable by 1.58 kcal/mol. The barrier to internal rotation about the C6–C12 bond was computed and this low barrier (7.655 kcal/mol) was shown to be associated with the θ=90° conformation. The results of the present work indicate that orotic acid behaves as a free rotor in the C6–C12 bond region and both the syn- and anti conformations were equally probable. Fourier analysis of the internal rotation function was carried out. The results indicate that the stability of the syn- over the anti-form was not due to increased or tight conjugative interaction, but rather due to decreased dipole–dipole repulsion and bond moment's interactions that is of electrostatic nature. The electronic structures of all possible tautomeric forms of orotic acid and that of its zwitterion have been thoroughly investigated. Equilibrium geometries were determined and compared to that of orotic acid. Solvent effects were taken in consideration. The self-consistent reaction field model (SCRF) was adopted to estimate gross solvent effects. The keto-form of orotic acid has been shown to be more stable than any other tautomeric forms.

Background Chrysanthemic acid (CHA) is a major product from the photodecomposition of pyrethrin which is an important class of pesticide compounds. In the following paper, Hybrid density functional theory (DFT) calculations of the potential energy surface (PES) for three possible channels decomposition of chrysanthemic acid (cis-trans isomerization, rearrangement and fragmentation) have been carried at the B3LYP/6-311+G** level of theory. DFT was employed to optimize the geometry parameters of the reactants, transition states, intermediates and products based on detailed potential energy surfaces (PES). Results Our results suggest that all three pathways of CHA are endothermic. DFT calculations revealed that the activation barriers for cis-trans isomerization are low, leading to a thermodynamically favorable process than other two pathways. We also investigated the solvent effect on the PES using the polarizable continuum model (PCM). In addition, time-dependent density functional theory (TDDFT) calculations showed that these reactions occur in the ground state rather than in an excited state. Conclusion The rearrangement process seems to be more favorable than the decomposition of CHA to carbene formation. The solvent effect calculations indicated no changes in the shape of the PES with three continua (water, ethanol and cyclohexane), although the solvents tend to stabilize all of the species.

The complexes of orotic acid with Co(II), Ni(II), Fe(III), Cu(II), and Cd(II) were prepared and their stoichiometry were determined by elemental analysis. Co(II) and Ni(II) give complexes with orotic acid of 1:1 ratio whereas that of the remaining transition metals give complexes of 1:2 ratio. The stereochemistry of the studied metal complexes has been established by analyses of their electronic spectra and magnetic susceptibilities. The mode of bonding in the studied series of metal complexes was established via, analysis of their infrared spectra. The present analysis leads to the conclusion that all metal ions studied coordinate to orotic acid via N(1) and the adjacent carboxylate group. Thermal decomposition studies of orotic acid complexes have been carried out as to understand the status of water molecules present in these complexes as well as to know their general decomposition pattern. Theoretical investigation of the electronic structure of the studied metal complexes has been carried out. MO computations at the HF-level were performed. Charge density distribution, extent of distortion from regular geometry, dipole moment, and orientation were computed and discussed.