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Another effect of HB is the very strong mixing of the CO and
OH vibrations both with each other and with the skeletal
vibrations in 1a.
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The hydrogen bond in 9-hydroxyphenalen-1-one presents
several properties characteristic for strong low-barrier HBs:
san enhanced strength relative to traditional hydrogen bonds
sa computed double-minimum potential energy surface with
a low (ca. 10 kJ/mol) barrier, in agreement with the experi-
mentally observed proton tunneling
sa short distance between the hydrogen-donor and the
hydrogen-acceptor atoms
sa very high OH torsional (932 cm ) and a computed very
low OH stretching frequency, where the latter band shows a
continuum in both the IR and Raman spectra
The HB energy in 1a was estimated to be ca. 60 kJ/mol. On
the basis of a joint analysis of the energetics and molecular
geometry, the HB interaction can be classified as a border case
between traditional and short-strong hydrogen bonds. The
molecule undergoes substantial structural reorganization between
the equilibrium configuration and the transition state, most of
the changes in interatomic distances and bond angles being
localized in the area of the oxygen atoms.
The charge distribution refers to the predominantly ionic
character of the HB interaction with marginal differences
between the asymmetric (1a) and symmetric (1b) forms. The
increased charge separation in the keto-enol moiety upon HB
is reflected in the enhanced IR intensities of several fundamen-
tals. Another characteristic effect of HB on the vibrational
properties of 1 is the enhanced mixing of the CO and OH
vibrations with each other and with the skeletal modes.
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B3-LYP density functional in conjunction with a diffuse
polarized valence triple-ú basis set while the B3-P86 functional
tends to overestimate considerably the strong hydrogen-bonding
interaction.
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Acknowledgment. A.K. thanks gratefully the Japan Inter-
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an STA fellowship and the Hungarian Scientific Research
Foundation (OTKA No. T030053) and the Bolyai Foundation
for finantial support. Prof. G. Keresztury is thanked for the
Raman spectrum.
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