J. Baik et al., Structures, energetics, and spectra of fluoride-water clusters F-(H2O)(n),n = 1-6: Ab initio study, J CHEM PHYS, 110(18), 1999, pp. 9116-9127
F-(H2O)(n) (n=1-6) clusters have been studied using ab initio calculations.
This is an extensive work to search for various low-lying energy conformer
s, for example, including 13 conformers for n=6. Our predicted enthalpies a
nd free energies are in good agreement with experimental values. For n=4 an
d 6, both internal and surface structures are almost isoenergetic at 0 K, w
hile internal structures are favored with increasing temperature due to the
entropic effect. For n=5, the internal structure is favored at both 0 and
298 K under 1 atm. These are contrasted to the favored surface structures i
n other small aqua-halide complexes. The ionization potential, charge-trans
fer-to-solvent (CTTS) energy, and O-H stretching vibrational spectra are re
ported to facilitate future experimental work. Many-body interaction potent
ial analyses are presented to help improve the potential functions used in
molecular simulations. The higher order many-body interaction energies are
found to be important to compare the energetics of the various conformers a
nd compare the stability of the internal over the surface state. (C) 1999 A
merican Institute of Physics. [S0021-9606(99)30318-4].