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

Journal of Chemical Sciences

Li Xiao-Hong1¹  Li Wei-Bin²  Zhang Xian-Zhou³ 

[1] College of Physics and Engineering, Henan University of Science and Technology, Luoyang 471003 China$$;Department of Physics and Chemistry, Henan polytechnic University, Jiaozuo 454000 China$$;College of Physics and Information Engineering, Henan Normal University, Xinxiang 453007 China$$

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

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

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** 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.

【 授权许可】

Unknown