pKa prediction using group philicity.
ABSTRACT Acid-base dissociation constants (pK(a) values) are important in understanding the chemical, environmental and toxicological properties of molecules. Though various methods have been developed to predict pK(a) by experimental and theoretical models, prediction of pK(a) is still complicated. Hence, a new approach for predicting pK(a) using the group philicity concept has been attempted. Presence of known functional groups in a molecule is utilized as the most important indicator to predict pK(a). The power of this descriptor in describing pK(a) for the series of carboxylic acids, various substituted phenols, anilines, phosphoric acids, and alcohols is probed. Results reveal that the group electrophilicity is suitable for effectively predicting the pK(a) values.
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ABSTRACT: Structural, chemical, magnetic and thermodynamic properties of palladium clusters Pdn with n = 2–11 are studied using density functional methods. The average bond length, entropy, enthalpy and polarisability are observed to increase as the cluster grows in size. The binding energy per atom also increases with cluster size. Stability function and atom addition energy change predict that Pd4, Pd6 and Pd9 are relatively more stable than their neighbouring clusters. Electron affinity, electronegativity and electrophilicity values suggest that larger clusters have stronger tendency to accept electrons, thereby supporting the relative stability of Pd4 and Pd6. Chemical hardness is also seen to decrease with cluster size, which suggests that large clusters are more prone to changes in their electronic structure. The magnetic properties of these clusters are reported.Molecular Simulation 12/2014; 40(15). · 1.06 Impact Factor
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ABSTRACT: Chemistry is the science of bond making and bond breaking which requires redistribution of electron density among the reactant partners. Accordingly acid-base and redox reactions form cardinal components in all branches of chemistry, e.g., inorganic, organic, physical or biochemistry. That is the reason it forms an integral part of the undergraduate curriculum all throughout the globe. In an electronegativity (χ)- hardness (η) landscape diagram the diagonal χ = η line separates reducing agents from oxidizing agents as well as Lewis acids from Lewis bases. While electronegativity is related to the degree of electron transfer between two reactants, hardness is related to the resistance to that process. Accordingly the electronegativities of oxidizing agents/Lewis acids are generally greater than the corresponding hardness values and the reverse is true for reducing agents/Lewis bases. Electrophiles and nucleophiles are also expected to follow similar trends.Journal of Molecular Modeling 09/2013; · 1.98 Impact Factor
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ABSTRACT: In this paper, we study the protonation of pyridine and phosphinine derivatives. In particular, the geometries, the amount of charge transfer, and the nature of the created N-H and P-H bonds are discussed, underlying the fundamental differences between the phosphorus and the nitrogen atoms as proton acceptors. Conceptual density functional theory and Bader's quantum theory of atoms-in-molecules are notably used to rationalize these trends and to predict the overall energies of these prototype gas-phase acid-base reactions.Journal of Molecular Modeling 09/2013; 19:4049. · 1.98 Impact Factor