ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Second order Møller–Plesset perturbation theory and density functional theory are employed to localize several stationary points on the potential energy surface of the cyclic methanol tetramer. Two cyclic isomers are identified: one of S4 symmetry, with methyl groups in up-down-up-down configuration, and a second one of Ci symmetry, with the methyl groups in up-up-down-down configuration. The latter minimum is 360 cm−1 above the S4 minimum, with a barrier of 475 cm−1 separating them. These isomers give rise to four asymmetric OH modes around 3300 cm−1. A model of the concerted proton transfer, S4→D2d→S4 (D2d is the transition structure), yields an estimate of 0.7 cm−1 for the tunneling splitting of the totally symmetric OH stretch vibrational fundamental. Raman spectra would show evidence of this fundamental and help to identify admixtures of the Ci isomer. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1319647
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