arXiv subjects

R. Parthasarathi

Publications and source records attributed to R. Parthasarathi.

3 recordsLinked to original sources

arXiv2007

A Multiphilic Descriptor for Chemical Reactivity and Selectivity

In line with the local philicity concept proposed by Chattaraj et al. (Chattaraj, P. K.; Maiti, B.; Sarkar, U. J. Phys. Chem. A. 2003, 107, 4973) and a dual descriptor derived by Toro-Labbe and coworkers (Morell, C.; Grand, A.; Toro-Labbe, A. J. Phys. Chem. A. 2005, 109, 205), we propose a multiphilic descriptor. It is defined as the difference between nucleophilic (Wk+) and electrophilic (Wk-) condensed philicity functions. This descriptor is capable of simultaneously explaining the nucleophilicity and electrophilicity of the given atomic sites in the molecule. Variation of these quantities along the path of a soft reaction is also analyzed. Predictive ability of this descriptor has been successfully tested on the selected systems and reactions. Corresponding force profiles are also analyzed in some representative cases. Also, to study the intra- and intermolecular reactivities another related descriptor namely, the nucleophilicity excess (DelW-+) for a nucleophile, over the electrophilicity in it has been defined and tested on all-metal aromatic compounds.

physics.chem-ph↗

arXiv2006

Parabolic bundles on algebraic surfaces I- the Donaldson--Uhlenbeck compactification

The aim of this paper is to construct the parabolic version of the Donaldson--Uhlenbeck compactification for the moduli space of parabolic stable bundles on an algenraic surface with parabolic structures along a divisor with normal crossing singularities. We prove the non--emptiness of the moduli space of parabolic stable bundles of rank 2 and also prove the existence of components with smooth points.

math.AG↗

arXiv2005

Electrophilicity as a Possible Descriptor of the Kinetic Behaviour

An understanding of the precise nature of a chemical reactivity descriptor is of utmost interest to quantum chemists. In the present investigation an attempt has been made to analyze whether the electrophilicity index is a reliable descriptor of the kinetic behaviour. Relative experimental rates of Friedel- Crafts benzylation, acetylation and benzoylation reactions correlate well with the corresponding calculated electrophilicity values. Chlorination of various substituted ethylenes and nitration of toluene and chlorobenzene are studied as representative examples of electrophilic addition and substitution reactions respectively. The correlation is not very good to assess that which, however, improves drastically by removing a few data points to show that the electrophilicity is a kinetic quantity with inherent thermodynamic information. The correlation between the experimental and the calculated activation energies is studied for some Markovnikov and anti-Markovnikov addition reactions and is turned out to be reasonably well. Reaction electrophilicity, local electrophilicity and activation hardness are used together to provide a transparent picture of reaction rates as well as the orientation of aromatic electrophilic substitution reactions. Ambiguity in the definition of the electrophilicity is highlighted.

physics.chem-ph↗