Friday, 6 October 2006
South Ballroom (Binghamton Regency Hotel and Conference Center)
362

Proton transfer between methoxide and methanol in methanol

Joseph G. Livingston and Vincent F. DeTuri. Ithaca College, Ithaca, NY

Proton transfer processes are investigated between methoxide and methanol in a methanol cluster. The energetics and dynamics of proton transfer is modeled as a function of methanol cluster size as it approaches the solvent limit. The solvent limit is modeled by sequential addition of methanol molecules from n = 1-21, where CH3O(CH3OH)n. These computational studies will be applied to model proton transfer reactions between carbon acids and methoxide in methanol solvent. A two-level ONIOM method is employed to reduce computational cost without sacrificing accuracy. The real system is modeled at the PM3 level and the hydrogen bonding OH groups are modeled at the B3LYP/6-31+G(d,p) level. Asymmetric clusters were built with each methoxide/methanol solvated by three methanol molecules excluding those on the periphery of the cluster. Manipulating the cluster size and the location of the methanols allowed strategic varying of the number of solvating molecules around each methoxide, which was indexed (a,b,c). Preliminary results show that the methoxide is most stable where it is maximally solvated or where a+b+c is greatest. However, the energy barrier for translocating the methoxide is small enough to allow its movement about the interior of the cluster at room temperature. From this data it is thus plausible that a transient methoxide translocated to the periphery of the cluster precedes the proton transfer step from the carbon acid to the cluster. Future work will investigate this hypothesis.

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