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Internet Electronic Journal of Molecular Design - IEJMD, ISSN 1538-6414, CODEN IEJMAT
| ABSTRACT - Internet Electron. J. Mol. Des. May 2003, Volume 2, Number 5, 306-314 |
A Theoretical Study of Intermolecular Interaction and Hydrogen Bond
for Furan with HCl and CH4-nCln (n = 0-3)
Daiqian Xie and Jiang Li
Internet Electron. J. Mol. Des. 2003, 2, 306-314
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Abstract:
Furan has both the oxygen lone pair electrons and an
aromatic π-electron. The study of the interaction between furan
as a proton acceptor and a proton donor is important to
understand the properties of furan and the related hydrogen
bond. The geometries, intermolecular energies and
vibrational properties of the furan-HCl and
furan-CH4-nCln (n = 0-3)
complexes have been performed using the second
order Moller-Plesset perturbation theory. The NBO analysis
of the optimized geometries has also been performed. The
optimized geometries of furan-HCl and
furan-CH4-nCln (n = 0-3)
show both the C(Cl)-H...O and C(Cl)-H...π
interactions. In all of the optimized geometries of
furan-CH4-nCln (n = 0-3),
C-H bond lengths are shorten and vibrational
frequencies are blue-shifted, while for the furan-HCl
complex, C-H bond length is lengthened and vibrational
frequencies are red-shifted. The NBO analysis shows that, for
the furan-CH4-nCln (n = 0-3)
complexes, the charge transfer
from the lone pairs of the O atom to both σ*(CH)
antibonding MO and lone pairs of Cl atom, which is the important feature
for blue-shifted hydrogen bond. Both lone pairs and π
electrons of furan can be acted as a proton acceptor
interacting with a proton donor. Cl-H...O(π) is a
conventional hydrogen bond , while C-H...O(π) is a blue-shifted
hydrogen bond.
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