Ab initio molecular dynamics studies of the liquid-vapor interface of an HC1 solution

Hee Seung Lee, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

Ab initio molecular dynamics is used to investigate the propensity of the hydronium ion for the interface of an HC1 solution containing 1 HC1 and 96 water molecules in a slab geometry. Unconstrained trajectories in the NVT and NVE ensemble reveal a clear preference of the hydronium ion for the interfacial region and several qualitative spectral features of interfacial hydronium ions. Orientational distribution functions indicate that the C 3 axis of the hydronium is tilted with respect to the surface normal, thereby allowing surface proton transfer reactions to occur. Finally, constrained simulations combined with thermodynamic integration are used to compute the potential of mean force for the transfer of the hydronium from the bulk to the interface and into the gas phase as a pure H 30 +. The potential of mean force is found to exhibit a shallow free energy minimum of roughly 1.3 kcal/mol with respect to the bulk, in good agreement with very recent calculations based on polarizable force fields and empirical valence bond potentials.

Original languageEnglish (US)
Pages (from-to)2144-2151
Number of pages8
JournalJournal of Physical Chemistry A
Volume113
Issue number10
DOIs
StatePublished - Mar 12 2009

Fingerprint

hydronium ions
liquid-vapor interfaces
Molecular Dynamics Simulation
Molecular dynamics
Vapors
molecular dynamics
Liquids
Proton transfer
Thermodynamics
field theory (physics)
Free energy
Distribution functions
Protons
slabs
Gases
distribution functions
free energy
Trajectories
trajectories
vapor phases

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Ab initio molecular dynamics studies of the liquid-vapor interface of an HC1 solution. / Lee, Hee Seung; Tuckerman, Mark.

In: Journal of Physical Chemistry A, Vol. 113, No. 10, 12.03.2009, p. 2144-2151.

Research output: Contribution to journalArticle

@article{e0d3fc9043fb4a758856c8a8969556d9,
title = "Ab initio molecular dynamics studies of the liquid-vapor interface of an HC1 solution",
abstract = "Ab initio molecular dynamics is used to investigate the propensity of the hydronium ion for the interface of an HC1 solution containing 1 HC1 and 96 water molecules in a slab geometry. Unconstrained trajectories in the NVT and NVE ensemble reveal a clear preference of the hydronium ion for the interfacial region and several qualitative spectral features of interfacial hydronium ions. Orientational distribution functions indicate that the C 3 axis of the hydronium is tilted with respect to the surface normal, thereby allowing surface proton transfer reactions to occur. Finally, constrained simulations combined with thermodynamic integration are used to compute the potential of mean force for the transfer of the hydronium from the bulk to the interface and into the gas phase as a pure H 30 +. The potential of mean force is found to exhibit a shallow free energy minimum of roughly 1.3 kcal/mol with respect to the bulk, in good agreement with very recent calculations based on polarizable force fields and empirical valence bond potentials.",
author = "Lee, {Hee Seung} and Mark Tuckerman",
year = "2009",
month = "3",
day = "12",
doi = "10.1021/jp809236c",
language = "English (US)",
volume = "113",
pages = "2144--2151",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Ab initio molecular dynamics studies of the liquid-vapor interface of an HC1 solution

AU - Lee, Hee Seung

AU - Tuckerman, Mark

PY - 2009/3/12

Y1 - 2009/3/12

N2 - Ab initio molecular dynamics is used to investigate the propensity of the hydronium ion for the interface of an HC1 solution containing 1 HC1 and 96 water molecules in a slab geometry. Unconstrained trajectories in the NVT and NVE ensemble reveal a clear preference of the hydronium ion for the interfacial region and several qualitative spectral features of interfacial hydronium ions. Orientational distribution functions indicate that the C 3 axis of the hydronium is tilted with respect to the surface normal, thereby allowing surface proton transfer reactions to occur. Finally, constrained simulations combined with thermodynamic integration are used to compute the potential of mean force for the transfer of the hydronium from the bulk to the interface and into the gas phase as a pure H 30 +. The potential of mean force is found to exhibit a shallow free energy minimum of roughly 1.3 kcal/mol with respect to the bulk, in good agreement with very recent calculations based on polarizable force fields and empirical valence bond potentials.

AB - Ab initio molecular dynamics is used to investigate the propensity of the hydronium ion for the interface of an HC1 solution containing 1 HC1 and 96 water molecules in a slab geometry. Unconstrained trajectories in the NVT and NVE ensemble reveal a clear preference of the hydronium ion for the interfacial region and several qualitative spectral features of interfacial hydronium ions. Orientational distribution functions indicate that the C 3 axis of the hydronium is tilted with respect to the surface normal, thereby allowing surface proton transfer reactions to occur. Finally, constrained simulations combined with thermodynamic integration are used to compute the potential of mean force for the transfer of the hydronium from the bulk to the interface and into the gas phase as a pure H 30 +. The potential of mean force is found to exhibit a shallow free energy minimum of roughly 1.3 kcal/mol with respect to the bulk, in good agreement with very recent calculations based on polarizable force fields and empirical valence bond potentials.

UR - http://www.scopus.com/inward/record.url?scp=63849088573&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=63849088573&partnerID=8YFLogxK

U2 - 10.1021/jp809236c

DO - 10.1021/jp809236c

M3 - Article

VL - 113

SP - 2144

EP - 2151

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 10

ER -