Articles written in Journal of Chemical Sciences

    • Interactions between metal cations with $ H_{2}$ in the $ M^{+}$-$ H_{2}$ complexes: Performance of DFT and DFT-D methods


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      The interactions between metal cations $(Ni^{+}$, $Cu^{+}$, $Zn^{+})$ and $H_{2}$ molecule have been investigatedin detail using dispersion-corrected and -uncorrected double hybrid density functional (DHDF), gradient correcteddensity functional, ordinary density functional and CCSD(T) methods in conjunction with the correlationconsistent triple-ζ quality basis sets. Structural properties, depth of the potential well and dissociationenergies are calculated using DFT, DFT-D and CCSD(T) methods and are compared with experimental results.A comparative analysis has been made among DFT, DFT-D and CCSD(T) methods with respect to experiments.The energy components of the interaction energy have been estimated by the symmetry-adapted perturbationtheory (SAPT) to analyze the effect of various components on the interaction of the complexes. Thedispersion-corrected DHDF, mPW2PLYP-D method shows the best agreement with the experimental values.An NBO analysis has been performed to understand the orbital participation in metal ligand interaction andcharge transfer process in these complexes.

    • Solvolysis of organophosphorus pesticide parathion with simple and α nucleophiles: a theoretical study


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      Density functional theory (DFT) has been used to study the solvolysis process of the organophosphorus compound, O,O-diethyl p-nitrophenyl thiophosphate (Parathion, PTH) with α-nucleophiles [hydroxylamine anion (NH2O), hydroperoxide (HOO) and simple nucleophile methylthiolate (CH3S) in both gas and aqueous phases. Formation of a trigonal bipyramidal intermediate at the phosphorus center followed by elimination of leaving group is considered to be the major solvolyzed pathway through addition-elimination scheme. In this study, although there are two possible orientations for incoming nucleophiles with respect to the substrate, the present reaction mechanism is found to be independent of this relative orientation. The proposed addition-elimination mechanism has been first explored here. The results indicate that the α-effect is observed in presence of solvent. Free energy barriers for NH2O and HOO are comparable and lower than that for the simple nulcleophile, CH3S. An important physical insight of this study is that there is a significant influence of the reaction medium on the nucleophilic reaction for solvolysis of PTH irrespective of the relative orientation of incoming nucleophile group.

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