• The solvent and substituent effects on bond dissociation energies of NO-donor molecules containing the N-NO bond

• # Fulltext

https://www.ias.ac.in/article/fulltext/jcsc/122/04/0521-0527

• # Keywords

Bond dissociation energy; density functional theory; NO-donor molecule; geometry optimization.

• # Abstract

Quantum chemical calculations are used to estimate the equilibrium N-NO bond dissociation energies (BDEs) for 15 NO-donor molecules in acetonitrile. These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86) methods together with 6-31G∗∗ basis set. The basis set superposition error (BSSE) and zero-point vibrational energy (ZPVE) are considered. The results are compared with the available experimental results. It is demonstrated that B3LYP/6-31G$^{\ast\ast}$ is accurate to compute the reliable BDEs for the NO-donor molecules. The solvent effects on the N-NO BDEs are analysed and the result shows that the N-NO BDEs in a vacuum computed by B3P86/6-31G∗∗ method are the closest to the computed values in acetontrile and the average solvent effect is 0.78 kcal/mol. Subsequently, the substituent effects on the N-NO BDEs are further analysed and it is found that electron donating group stabilizes the radical and as a result BDE decreases; whereas electron withdrawing group stabilizes the ground state of the molecule and thus increases the BDE.

• # Author Affiliations

1. College of Physics and Engineering, Henan University of Science and Technology, Luoyang 471003 China
2. Department of Physics and Chemistry, Henan polytechnic University, Jiaozuo 454000 China
3. College of Physics and Information Engineering, Henan Normal University, Xinxiang 453007 China

• # Journal of Chemical Sciences

Volume 134, 2022
All articles
Continuous Article Publishing mode

• # Editorial Note on Continuous Article Publication

Posted on July 25, 2019