Kr. Liedl et al., NEW INSIGHTS INTO THE DYNAMICS OF CONCERTED PROTON TUNNELING IN CYCLIC WATER AND HYDROGEN-FLUORIDE CLUSTERS, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(26), 1997, pp. 4707-4716
The concerted proton transfer hypersurface of cyclic water and hydroge
n fluoride clusters has been described by high-level molecular quantum
mechanical calculations. For the cyclic water clusters the concerted
proton transfer transition states have been investigated for the first
time with methods including treatment of dynamic electron correlation
. The crucial importance of dynamic electron correlation for the barri
er heights is demonstrated, A detailed analysis of the minimum energy
path has been performed. The reaction swath of the concerted proton tr
ansfer was examined indicating a reasonable description by harmonic ap
proximation of the energy hypersurface. Transfer rates have been calcu
lated by means of variational transition state theory with interpolate
d corrections (VTST-IC) and dual-level direct dynamics (DLDD), both wi
th semiclassical tunneling corrections. Tunneling is very efficient in
the concerted proton exchange reaction of the cyclic hydrogen-bonded
clusters under investigation. Rate constants for the concerted exchang
e of hydrogens in important hydrogen fluoride vapor phase species are
reported for the first time. In the hydrogen fluoride tetramer and pen
tamer the concerted proton exchange of four and five protons, respecti
vely, takes place with reaction rates that an comparable with the conc
erted exchange rates in carboxylic acid dimers and is not hindered by
the large number of simultanously moving protons. The concerted proton
exchange rates in the studied water clusters are comparably low becau
se of higher exchange barriers. It is shown that hydrogen fluoride clu
sters can be used to a large extent as ''simplified'' experimental and
theoretical models for water clusters.