Temporal evolution of local and global hardness during an ion-atom collision process has been studied within a quantum fluid density functional framework. A dynamical variant of the maximum hardness principle has been found to be operative. Entropy maximises in the encounter regime. Time dependence of density and its laplacian provides important insights into the collision processvis-a-vis the hardness maximisation.

Attempts are made to gain insights into the effect of confinement of noble gas atoms on their various reactivity indices. Systems become harder, less polarizable and difficult to excite as the compression increases. Ionization also causes similar effects. A quantum fluid density functional technique is adopted in order to study the dynamics of reactivity parameters during a collision between protons and He atoms in different electronic states for various projectile velocities and impact parameters. Dynamical variants of the principles of maximum hardness, minimum polarizability and maximum entropy are found to be operative.

Inter-relationships between the electrophilicity index (Ω), Hammett constant (ó_p@#@) and nucleusindependent chemical shift (NICS (1) — NICS value one ångstrom above the ring centre) have been investigated for a series of meta- and para-substituted benzoic acids. Good linear relationships between Hammett constant vs electrophilicity and Hammett constant vs NICS (1) values have been observed. However, the variation of NICS (1) against CO shows only a low correlation coefficient.

The applicability of DFT-based descriptors for the development of toxicological structure-activity relationships is assessed. Emphasis in the present study is on the quality of DFT-based descriptors for the development of toxicological QSARs and, more specifically, on the potential of the electrophilicity concept in predicting toxicity of benzidine derivatives and the series of polyaromatic hydrocarbons (PAH) expressed in terms of their biological activity data (pIC₅₀). First, two benzidine derivatives, which act as electron-donating agents in their interactions with biomolecules are considered. Overall toxicity in general and the most probable site of reactivity in particular are effectively described by the global and local electrophilicity parameters respectively. Interaction of two benzidine derivatives with nucleic acid (NA) bases/selected base pairs is determined using Parr’s charge transfer formula. The experimental biological activity data (pIC₅₀) for the family of PAH, namely polychlorinated dibenzofurans (PCDF), poly-halogenated dibenzo-p-dioxins (PHDD) and polychlorinated biphenyls (PCB) are taken as dependent variables and the HF energy (E), along with DFT-based global and local descriptors, viz., electrophilicity index (Ω) and local electrophilic power (Ω⁺) respectively are taken as independent variables. Fairly good correlation is obtained showing the significance of the selected descriptors in the QSAR on toxins that act as electron acceptors in the presence of biomolecules. Effects of population analysis schemes in the calculation of Fukui functions as well as that of solvation are probed. Similarly, some electron-donor aliphatic amines are studied in the present work. We see that global and local electrophilicities along with the HF energy are adequate in explaining the toxicity of several substances, both electron donors or acceptors when they interact with biosystems, in gas as well as solution phases.

A transition from regular to chaotic behaviour in the dynamics of a classical Henon-Heiles oscillator in the presence of an external field is shown to have a similar quantum signature when studied using the pertaining phase portraits and the associated Kolmogorov-Sinai-Lyapunov entropies obtained through the corresponding Bohmian trajectories.

Several sandwich-like metal clusters have been studied at the B3LYP/6-311 + G^∗ level of theory. Bonding and reactivity have been analysed through various geometrical parameters and conceptual density functional theory based global reactivity descriptors. Aromaticity patterns have been understood in terms of the associated nucleus independent chemical shift values. Possibility of bond-stretch isomerism in some doped clusters is explored. Preferable sites for electrophilic and nucleophilic attacks have been identified using different local reactivity descriptors.