Stabilization of metastable hydrogen trioxide (HOOOH) and the hydrotrioxyl radical (HOOO•) by complexation with sulfuric acid. A theoretical study

被引：12

作者：

Cannon, Daniel ^{[1
]}

Tuttle, Tell ^{[1
]}

Koller, Joze ^{[2
]}

Plesnicar, Bozo ^{[2
]}

机构：

[1] Univ Strathclyde, Dept Pure & Appl Chem, WestCHEM, Glasgow G1 1XL, Lanark, Scotland

[2] Univ Ljubljana, Fac Chem & Chem Technol, Dept Chem, Ljubljana 1000, Slovenia

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2013年 / 1010卷

基金：

英国工程与自然科学研究理事会;

关键词：

Computational; Atmospheric; DFT; CCSD(T); H2SO4; Hydrotrioxides; MOLECULAR-ORBITAL METHODS; SET SUPERPOSITION ERROR; GAUSSIAN-TYPE BASIS; ROTATIONAL SPECTRUM; WATER; PEROXIDE; HO3; OZONATION; CLUSTERS; DECOMPOSITION;

D O I：

10.1016/j.comptc.2013.01.009

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The formation of bimolecular complexes of HOOOH and the HOOO center dot radical with sulfuric acid (H2SO4-HOOOH, H2SO4-HOOO center dot) has been investigated by using DFT (B3LYP/6-311++G(3df,3pd)) and CCSD(T)-F12 methods. For the first time the structures and the binding energies (BEs) for the various isomeric hydrogen-bonded complexes have been reported. The results reveal an unusually stable H2SO4-HOOOH eight-membered ring structure with two relatively strong hydrogen bonds, and with a calculated BE (CCSD(T)-F12) of 12.7 kcal mol(-1). This is equivalent to the BE in the H2SO4-HOOH complex investigated at the same theoretical level. The complexation of HOOO center dot with H2SO4 stabilizes this metastable polyoxide intermediate by about 10.0 kcal mol(-1). (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：19 / 24

页数：6

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