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

Daniel Cannon, Tell Tuttle, J. Koller, B. Plesnicar

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The formation of bimolecular complexes of HOOOH and the HOOOﰀ radical with sulfuric acid (H2SO4– HOOOH, H2SO4–HOOOﰀ) 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 molﰁ1. This is equivalent to the BE in the H2SO4–HOOH complex investigated at the same theoretical level. The complexation of HOOOﰀ with H2SO4 stabilizes this metastable polyoxide intermediate by about 10.0 kcal molﰁ1.
Original languageEnglish
Pages (from-to)19-24
Number of pages6
JournalComputational and Theoretical Chemistry
Volume1010
DOIs
Publication statusPublished - 15 Apr 2013

Fingerprint

sulfuric acid
Complexation
Binding energy
Hydrogen
Theoretical Models
Stabilization
stabilization
binding energy
hydrogen
ring structures
Discrete Fourier transforms
Hydrogen bonds
hydrogen bonds
HOOO radical

Keywords

  • computational
  • atmospheric
  • hydrotrioxides
  • H2SO4
  • DFT

Cite this

@article{c6206daee7354454b7fd456801e07597,
title = "Stabilization of metastable hydrogen trioxide (HOOOH) and the hydrotrioxyl radical (HOOOradical dot) by complexation with sulfuric acid. A theoretical study",
abstract = "The formation of bimolecular complexes of HOOOH and the HOOOﰀ radical with sulfuric acid (H2SO4– HOOOH, H2SO4–HOOOﰀ) 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 molﰁ1. This is equivalent to the BE in the H2SO4–HOOH complex investigated at the same theoretical level. The complexation of HOOOﰀ with H2SO4 stabilizes this metastable polyoxide intermediate by about 10.0 kcal molﰁ1.",
keywords = "computational, atmospheric, hydrotrioxides, H2SO4, DFT",
author = "Daniel Cannon and Tell Tuttle and J. Koller and B. Plesnicar",
year = "2013",
month = "4",
day = "15",
doi = "10.1016/j.comptc.2013.01.009",
language = "English",
volume = "1010",
pages = "19--24",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",

}

TY - JOUR

T1 - Stabilization of metastable hydrogen trioxide (HOOOH) and the hydrotrioxyl radical (HOOOradical dot) by complexation with sulfuric acid. A theoretical study

AU - Cannon, Daniel

AU - Tuttle, Tell

AU - Koller, J.

AU - Plesnicar, B.

PY - 2013/4/15

Y1 - 2013/4/15

N2 - The formation of bimolecular complexes of HOOOH and the HOOOﰀ radical with sulfuric acid (H2SO4– HOOOH, H2SO4–HOOOﰀ) 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 molﰁ1. This is equivalent to the BE in the H2SO4–HOOH complex investigated at the same theoretical level. The complexation of HOOOﰀ with H2SO4 stabilizes this metastable polyoxide intermediate by about 10.0 kcal molﰁ1.

AB - The formation of bimolecular complexes of HOOOH and the HOOOﰀ radical with sulfuric acid (H2SO4– HOOOH, H2SO4–HOOOﰀ) 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 molﰁ1. This is equivalent to the BE in the H2SO4–HOOH complex investigated at the same theoretical level. The complexation of HOOOﰀ with H2SO4 stabilizes this metastable polyoxide intermediate by about 10.0 kcal molﰁ1.

KW - computational

KW - atmospheric

KW - hydrotrioxides

KW - H2SO4

KW - DFT

UR - http://www.scopus.com/inward/record.url?scp=84874414349&partnerID=8YFLogxK

U2 - 10.1016/j.comptc.2013.01.009

DO - 10.1016/j.comptc.2013.01.009

M3 - Article

VL - 1010

SP - 19

EP - 24

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

ER -