Theoretical Investigations on Mechanisms and Pathways of C₂H₅O₂ with BrO Reaction in the Atmosphere.

Chenggang Lu,Yizhen Tang,Xunshuai Qu,Wei Zhang,Zhihao Fu

doi:10.3390/molecules23061268

Abstract

In this work, feasible mechanisms and pathways of the C2H5O2 + BrO reaction in the atmosphere were investigated using quantum chemistry methods, i.e., QCISD(T)/6-311++G(2df,2p)//B3LYP/6-311++G(2df,2p) levels of theory. Our result indicates that the title reaction occurs on both the singlet and triplet potential energy surfaces (PESs). Kinetically, singlet C2H5O3Br and C2H5O2BrO were dominant products under the atmospheric conditions below 300 K. CH3CHO2 + HOBr, CH3CHO + HOBrO, and CH3CHO + HBrO2 are feasible to a certain extent thermodynamically. Because of high energy barriers, all products formed on the triplet PES are negligible. Moreover, time-dependent density functional theory (TDDFT) calculation implies that C2H5O3Br and C2H5O2BrO will photolyze under the sunlight.

Highlights

With more and more attention paid to atmospheric environments, researchers focused on the reactions that will increase or produce pollution
The rate constants of BrO reacting with HO2 [8,9,10], CH3 O2 [11,12,15] and C2 H5 O2 [16] radicals were determined by several groups
C2 H5 O2 + BrO reaction from experiments, and no literature is available from theoretical investigations yet

Summary

Introduction

With more and more attention paid to atmospheric environments, researchers focused on the reactions that will increase or produce pollution. ClO, the reactions of BrO with peroxy radicals RO2 (R is organic group), such as HO2 and CH3 O2, have been investigated extensively by experimental and theoretical methods [3,4,5,6,7,8,9,10,11,12,13,14,15,16]. The rate constants of BrO reacting with HO2 [8,9,10], CH3 O2 [11,12,15] and C2 H5 O2 [16] radicals were determined by several groups. C2 H5 O2 + BrO reaction from experiments, and no literature is available from theoretical investigations yet. The following channels were proposed by Sakamoto [16]

Methods

Results

Conclusion