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          Institute: MPI für Festkörperforschung     Collection: FKF Publikationen 2002     Display Documents

ID: 7273.0, MPI für Festkörperforschung / FKF Publikationen 2002
The nature and transport mechanism of hydrated hydroxide ions in aqueous solution
Authors:Tuckerman, M. E.; Marx, D.; Parrinello, M.
Date of Publication (YYYY-MM-DD):2002
Title of Journal:Nature
Issue / Number:6892
Start Page:925
End Page:929
Review Status:Peer-review
Audience:Not Specified
Abstract / Description:Compared to other ions, protons (H+) and hydroxide ions (OH-)
exhibit anomalously high mobilities in aqueous solutions(1). On
a qualitative level, this behaviour has long been explained by
'structural diffusion'-the continuous interconversion between
hydration complexes driven by fluctuations in the solvation
shell of the hydrated ions. Detailed investigations have led to
a clear understanding of the proton transport mechanism at the
molecular level(2-8). In contrast, hydroxide ion mobility in
basic solutions has received far less attention(2,3,9,10), even
though bases and base catalysis play important roles in many
organic and biochemical reactions and in the chemical industry.
The reason for this may be attributed to the century-old
notion(11) that a hydrated OH- can be regarded as a water
molecule missing a proton, and that the transport mechanism of
such a 'proton hole' can be inferred from that of an excess
proton by simply reversing hydrogen bond polarities(11-18).
However, recent studies(2,3) have identified OH- hydration
complexes that bear little structural similarity to proton
hydration complexes. Here we report the solution structures and
transport mechanisms of hydrated hydroxide, which we obtained
from first-principles computer simulations that explicitly
treat quantum and thermal fluctuations of all nuclei(19-21). We
find that the transport mechanism, which differs significantly
from the proton hole picture, involves an interplay between the
previously identified hydration complexes(2,3) and is strongly
influenced by nuclear quantum effects.
External Publication Status:published
Document Type:Article
Communicated by:Michaela Asen-Palmer
Affiliations:MPI für Festkörperforschung
External Affiliations:; NYU, Dept Chem, 4 Washington Pl, New York, NY 10003 USA
; NYU, Courant Inst Math Sci, New York, NY 10003 USA
; Ruhr Univ Bochum, Lehrstuhl Theoret Chem, D-44780 Bochum, Germany
; Max Planck Inst Festkorperforsch, D-70569 Stuttgart, Germany
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