Density Functional Theory Studies on the Addition and Abstraction Reactions of OH Radical with Benzoate Anion

Nobuaki Tanaka,Shigeo Itoh

doi:10.4236/ojpc.2013.31002

Nobuaki Tanaka, Shigeo Itoh

Open Access

https://doi.org/10.4236/ojpc.2013.31002

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Abstract

The addition and abstraction reactions of OH radical with benzoate anion are investigated by density functional theory calculations that include solvent effects using UB3LYP, UCAM-B3LYP, UmPW1PW91 and UM06-2X functionals with the 6-311++G(2d,2p) basis set. Geometry optimizations of the reactants, products and transition state species are performed for the possible reaction paths. For the addition reactions, those targeting the ipso-, ortho-, meta- and para-carbons are predicted to be exoergic. The H-atom abstraction reactions from ortho, meta and para positions are also predicted to be exoergic. On the basis of the rate constants calculated by means of the transition state theory, the H-atom abstraction reaction from the ortho position is determined to be the favored path followed by the ortho OH addition reaction.

Highlights

Sodium salicylate is known as a good phosphor under the x-ray and vacuum ultraviolet excitation [1]
The addition and abstraction reactions of OH radical with benzoate anion are investigated by density functional theory calculations that include solvent effects using UB3LYP, UCAM-B3LYP, UmPW1PW91 and UM06-2X functionals with the 6-311++G(2d,2p) basis set
On the basis of the rate constants calculated by means of the transition state theory, the H-atom abstraction reaction from the ortho position is determined to be the favored path followed by the ortho OH addition reaction

Summary

Introduction

Sodium salicylate is known as a good phosphor under the x-ray and vacuum ultraviolet excitation [1]. Peräkylä et al [5] have theoretically studied the reactivity of benzoate towards OH addition reaction at the ROHF/6-31G(d) and ROMP2/6-31G(d) levels including solvent effects on the basis of the qualitative frontier molecular orbital theory and compared the stability of the isomeric OH adducts of benzoate. They revealed the correlation between the kinetic reactivity and the thermodynamic stabilities of the addition products.

Computational Methods

OH Addition Reaction

H-Atom Abstraction Reaction

Conclusion