Electrophilicity Equalization Principle

A new electronic structure principle, viz., the principle of electrophilicity equalization is proposed. An analytical justification as well as a numerical support for the same is provided.Comment: 9 pages, 2 table

Minimum Magnetizability Principle

A new electronic structure principle, viz. the minimum magnetizability principle (MMP) has been proposed and also has been verified through ab initio calculations, to extend the domain of applicability of the conceptual density functional theory (DFT) in explaining the magnetic interactions and magnetochemistry. This principle may be stated as, "A stable configuration/conformation of a molecule or a favorable chemical process is associated with a minimum value of the magnetizability". It has also been shown that a soft molecule is easily polarizable and magnetizable than a hard one.Comment: 2 Pages, 3 Figure

Aromaticity in Polyacene Analogues of Inorganic Ring Compounds

The aromaticity in the polyacene analogues of several inorganic ring compounds (BN-acenes, CN-acenes, BO-acenes and Na6-acenes) is reported here for the first time. Conceptual density functional theory based reactivity descriptors and the nucleus independent chemical shift (NICS) values are used in this analysis.Comment: 4 pages, 2 figures, 2 table

Hydrogen (H2) Storage in Clathrate Hydrates

Structure, stability and reactivity of clathrate hydrates with or without hydrogen encapsulation are studied using standard density functional calculations. Conceptual density functional theory based reactivity descriptors and the associated electronic structure principles are used to explain the hydrogen storage properties of clathrate hydrates. Different thermodynamic quantities associated with H2-trapping are also computed. The stability of the H2-clathrate hydrate complexes increases upon the subsequent addition of hydrogen molecules to the clathrate hydrates. The efficacy of trapping of hydrogen molecules inside the cages of clathrate hydrates depends upon the cavity sizes and shapes of the clathrate hydrates. Computational studies reveal that 512 and 51262 structures are able to accommodate up to two H2 molecules whereas 51268 can accommodate up to six hydrogen molecules.Comment: 21 pages, 5 figures, 6 table

A philicity based analysis of adsorption of small molecules in zeolites

Adsorption of small molecules like CH4, CO and NH3 into the acid sites of zeolites is analysed as an interaction between an electrophile and a nucleophile. Global reactivity descriptors like softness and electrophilicity, and local reactivity descriptors like the Fukui function, local softness and local philicity are calculated within density functional as well as Hartree-Fock frameworks using both Mulliken and Hirshfeld population analysis schemes. The HSAB principle and the best electrophile-nucleophile combination suggest that the reaction between the NH3 and Bronsted acid site of the zeolite is the strongest. Interaction between the zeolite and a small probe molecule takes place through the most electrophilic atom of one with the most nucleophilic atom of the other. This result is in conformity with those provided by the frontier orbital theory and the local HSAB principle