Ab initio molecular dynamics study of the aqueous HOO- ion

Zhonghua Ma, David Anick, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

The properties of the hydroperoxide anion, HOO-, in water play a key role in many biological systems and industrial processes. However the dynamics of HOO- and its solvation shell are largely unknown. We have undertaken an ab initio molecular dynamics study of aqueous HOO- at ambient temperature in liquid water. Two solvation structures for the hydroperoxide anion account for 90% or more of the configurations in a 25 ps NVT run at 300 K: these have four hydrogen bond donors to the terminal oxygen atom of HOO- and either one or two hydrogen bond donors to its middle oxygen atom. The H of HOO- is essentially always a donor in an H-bond to a water molecule. Two structures with three donors to the terminal O and either one or two at the middle O are also important. A set of five NVE runs totaling 74 ps found considerable variability in the proportions of time spent in each type of solvation pattern. Mean lifetimes of these patterns ranged from 54 to 109 fs, after which the complexes were observed to transform into different, sometimes less favorable structures. Analysis of the electronic structure associated with different solvation patterns indicates that a traditional Lewis-type picture of hydrogen bonding at the middle oxygen and non-Lewis behavior at the terminal oxygen coexist in aqueous HOO-. The non-Lewis character of the terminal oxygen is compared to similar observations of the oxygen in the hydrated hydroxide ion from previous ab initio molecular dynamics of OH-(aq).

Original languageEnglish (US)
Pages (from-to)7937-7945
Number of pages9
JournalJournal of Physical Chemistry B
Volume118
Issue number28
DOIs
StatePublished - Jul 17 2014

Fingerprint

Molecular Dynamics Simulation
solvation
Molecular dynamics
Solvation
Ions
Oxygen
molecular dynamics
oxygen
oxygen atoms
Hydrogen bonds
ions
water
hydrogen bonds
anions
Hydrogen Peroxide
Anions
Water
Hydrogen
Negative ions
ambient temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films
  • Medicine(all)

Cite this

Ab initio molecular dynamics study of the aqueous HOO- ion. / Ma, Zhonghua; Anick, David; Tuckerman, Mark.

In: Journal of Physical Chemistry B, Vol. 118, No. 28, 17.07.2014, p. 7937-7945.

Research output: Contribution to journalArticle

Ma, Zhonghua ; Anick, David ; Tuckerman, Mark. / Ab initio molecular dynamics study of the aqueous HOO- ion. In: Journal of Physical Chemistry B. 2014 ; Vol. 118, No. 28. pp. 7937-7945.
@article{392c66c345094d1d91da477cadd23007,
title = "Ab initio molecular dynamics study of the aqueous HOO- ion",
abstract = "The properties of the hydroperoxide anion, HOO-, in water play a key role in many biological systems and industrial processes. However the dynamics of HOO- and its solvation shell are largely unknown. We have undertaken an ab initio molecular dynamics study of aqueous HOO- at ambient temperature in liquid water. Two solvation structures for the hydroperoxide anion account for 90{\%} or more of the configurations in a 25 ps NVT run at 300 K: these have four hydrogen bond donors to the terminal oxygen atom of HOO- and either one or two hydrogen bond donors to its middle oxygen atom. The H of HOO- is essentially always a donor in an H-bond to a water molecule. Two structures with three donors to the terminal O and either one or two at the middle O are also important. A set of five NVE runs totaling 74 ps found considerable variability in the proportions of time spent in each type of solvation pattern. Mean lifetimes of these patterns ranged from 54 to 109 fs, after which the complexes were observed to transform into different, sometimes less favorable structures. Analysis of the electronic structure associated with different solvation patterns indicates that a traditional Lewis-type picture of hydrogen bonding at the middle oxygen and non-Lewis behavior at the terminal oxygen coexist in aqueous HOO-. The non-Lewis character of the terminal oxygen is compared to similar observations of the oxygen in the hydrated hydroxide ion from previous ab initio molecular dynamics of OH-(aq).",
author = "Zhonghua Ma and David Anick and Mark Tuckerman",
year = "2014",
month = "7",
day = "17",
doi = "10.1021/jp5008335",
language = "English (US)",
volume = "118",
pages = "7937--7945",
journal = "Journal of Physical Chemistry B",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "28",

}

TY - JOUR

T1 - Ab initio molecular dynamics study of the aqueous HOO- ion

AU - Ma, Zhonghua

AU - Anick, David

AU - Tuckerman, Mark

PY - 2014/7/17

Y1 - 2014/7/17

N2 - The properties of the hydroperoxide anion, HOO-, in water play a key role in many biological systems and industrial processes. However the dynamics of HOO- and its solvation shell are largely unknown. We have undertaken an ab initio molecular dynamics study of aqueous HOO- at ambient temperature in liquid water. Two solvation structures for the hydroperoxide anion account for 90% or more of the configurations in a 25 ps NVT run at 300 K: these have four hydrogen bond donors to the terminal oxygen atom of HOO- and either one or two hydrogen bond donors to its middle oxygen atom. The H of HOO- is essentially always a donor in an H-bond to a water molecule. Two structures with three donors to the terminal O and either one or two at the middle O are also important. A set of five NVE runs totaling 74 ps found considerable variability in the proportions of time spent in each type of solvation pattern. Mean lifetimes of these patterns ranged from 54 to 109 fs, after which the complexes were observed to transform into different, sometimes less favorable structures. Analysis of the electronic structure associated with different solvation patterns indicates that a traditional Lewis-type picture of hydrogen bonding at the middle oxygen and non-Lewis behavior at the terminal oxygen coexist in aqueous HOO-. The non-Lewis character of the terminal oxygen is compared to similar observations of the oxygen in the hydrated hydroxide ion from previous ab initio molecular dynamics of OH-(aq).

AB - The properties of the hydroperoxide anion, HOO-, in water play a key role in many biological systems and industrial processes. However the dynamics of HOO- and its solvation shell are largely unknown. We have undertaken an ab initio molecular dynamics study of aqueous HOO- at ambient temperature in liquid water. Two solvation structures for the hydroperoxide anion account for 90% or more of the configurations in a 25 ps NVT run at 300 K: these have four hydrogen bond donors to the terminal oxygen atom of HOO- and either one or two hydrogen bond donors to its middle oxygen atom. The H of HOO- is essentially always a donor in an H-bond to a water molecule. Two structures with three donors to the terminal O and either one or two at the middle O are also important. A set of five NVE runs totaling 74 ps found considerable variability in the proportions of time spent in each type of solvation pattern. Mean lifetimes of these patterns ranged from 54 to 109 fs, after which the complexes were observed to transform into different, sometimes less favorable structures. Analysis of the electronic structure associated with different solvation patterns indicates that a traditional Lewis-type picture of hydrogen bonding at the middle oxygen and non-Lewis behavior at the terminal oxygen coexist in aqueous HOO-. The non-Lewis character of the terminal oxygen is compared to similar observations of the oxygen in the hydrated hydroxide ion from previous ab initio molecular dynamics of OH-(aq).

UR - http://www.scopus.com/inward/record.url?scp=84904579593&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84904579593&partnerID=8YFLogxK

U2 - 10.1021/jp5008335

DO - 10.1021/jp5008335

M3 - Article

VL - 118

SP - 7937

EP - 7945

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 28

ER -