Electrostatic potential minimum of the aromatic ring as a measure of substituent constant.
The molecular electrostatic potential minimum (Vmin) observed for the arene pi system of a substituted benzene derivatives is found to correlate linearly with the substituent constant sigma(p) degrees . The use of Vmin as a measure of substituent effect is further confirmed by obtaining a linear correlation between Vmin and a thermodynamic measure of the substituent effect obtained from an isodesmic reaction scheme involving benzene derivatives. Vmin and the recently proposed electrostatic potential value at the nucleus of the para carbon atom (Vc) show a nearly identical trend toward quantification of substituent effects. Both quantities have been compared at three different density functional theory methods, viz. B3LYP/6-311+G(2d,2p), BPW91/6-311G(d,p), and B3LYP/aug-cc-pvtz, as well as the at the MP2/6-31+G(d,p) level of theory, showing remarkable consistency among them.
Suresh
Cherumuttathu H
CH
Computational Modeling and Simulation Section, Regional Research Laboratory (CSIR), Trivandrum 695 019, India. sureshch@gmail.com
Gadre
Shridhar R
SR