FT MICROWAVE SPECTROSCOPIC STUDY OF $(CH_{3})_{3}N\cdots HCN \cdots HCN$
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Date
2003
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
Rotational spectra of the hydrogen-bonded trimer $(CH_{3})_{3}N\cdots HCN \cdots HCN$ and10 isotopically substituted derivatives have been observed using Fourier transform microwave spectroscopy. The complex is a symmetric top with the atomic arrangements indicated above. A central focus of this work is to test the effect of microsolvation in promoting proton transfer across a strong hydrogen bond. Analysis of the rotational and quadrupole coupling constants will be presented, along with ab initio binding energy and geometry optimization results. Preliminary structural analysis indicates an $N \cdots H$ hydrogen bond contraction of approximately 0.08 {\AA} relative to the dimer $(CH_{3})_{3} N \cdots HCN$. Changes in the secondary hydrogen bond between the two HCN subunits lie within the experimental uncertainty for the $N \cdots H$ distance in HCN dimer. The effect of increasing the basicity of the amine in amine-HCN systems will be discussed in the context of previous work on the closely related system $H_{3}N \cdots HCN \cdots HCN^{a}$.
Description
$^{a}$R. S. Ruoff, T. Emilsson, C. Chuang,T. D. Klots,H. S. Gutowsky J Chem. Phys. 93(9), 6363, (1990).
Author Institution: Department of Chemistry, University of Minnesota; Department of Chemistry, St. Cloud State University
Author Institution: Department of Chemistry, University of Minnesota; Department of Chemistry, St. Cloud State University