Abstract
Fully optimized structures were calculated for (H2O)n, n=5 and 8, at the SCF (self-consistent field) level using the 4–31G and, for n=5, also 6–31G* basis sets. The n=5 cluster was found to have a cyclic structure with five H bonded and five free hydrogens. The n=8 minimum energy structure has almost D2d symmetry, with an approximately cubical oxygen framework and four tetrahedrally arranged free hydrogens; four of the water molecules are single- and four are double-hydrogen donors. Harmonic vibrational frequencies, IR and Raman intensities were calculated for n=5 and 8, as well as for the previously optimized n=2–4 clusters. The band positions and intensities in the 3000–3800 cm−1 region correlate well with IR predissociation spectra of (H2O)n clusters. The O–H stretching frequencies of single- and double-hydrogen donor water molecules are relatively well separated from each other, and both from the frequency region of the free O–H stretches, suggesting a new interpretation for some of the data. The low-frequency translational/librational modes of both n=5 and 8 show strong mixing with intramolecular stretching and bending. The stretch–stretch coupling constants for OH oscillators on different molecules kij(OH,OH) show a strong increase, and those for intramolecular coupling kii(OH,OH) a rapid decrease with increasing cluster size. For n≥5, kij(OH,OH)≫kii(OH,OH), implying that the cluster can be viewed as a supermolecule of strongly coupled O–H oscillators. The n=8 spectra show significant similarity to those of ice.
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Dates
| Type | When |
|---|---|
| Created | 23 years ago (July 26, 2002, 8:40 a.m.) |
| Deposited | 1 year, 6 months ago (Feb. 10, 2024, 9:10 a.m.) |
| Indexed | 1 month, 3 weeks ago (June 30, 2025, 7:26 a.m.) |
| Issued | 33 years, 4 months ago (April 1, 1992) |
| Published | 33 years, 4 months ago (April 1, 1992) |
| Published Print | 33 years, 4 months ago (April 1, 1992) |
@article{Knochenmuss_1992, title={Structures and vibrational spectra of water clusters in the self-consistent-field approximation}, volume={96}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.462734}, DOI={10.1063/1.462734}, number={7}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Knochenmuss, R. and Leutwyler, S.}, year={1992}, month=apr, pages={5233–5244} }