SIZING THE UBBELHODE EFFECT: THE ROTATIONAL SPECTRUM OF \textit{TERT}-BUTYLALCOHOL DIMER

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We measured the molecular beam Fourier transform microwave spectra of four isotopic species of of the dimer of \textit{tert}-butanol, that is C$_{4}$H$_{9}$-OH$\cdots$O(H)-C$_{4}$H$_{9}$, C$_{4}$H$_{9}$-OH$\cdots$O(D)-C$_{4}$H$_{9}$, C$_{4}$H$_{9}$-OD$\cdots$O(H)-C$_{4}$H$_{9}$, and C$_{4}$H$_{9}$-OD$\cdots$O(D)-C$_{4}$H$_{9}$. We observed that the H -- D isotopic substitution of the hydroxylic hydrogen participating in the O-H$\cdots$O Hydrogen bond in the \textit{tert}-butanol dimer produces an increase of the B and C rotational constants, according to the shrinkage of the O$\cdots$O distance, underlying and sizing the associated Ubbelhode effect. , 1955, 8, 71} The conformation and structure of the complex, and an estimation of the Ubbelhode effect have been obtained by combining the experimental data with the results of MP2/6-311++G** ab initio calculations.

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A.~R.~Ubbelhode, K.~J.~Gallagher, \textit{Acta Crystallogr.
Author Institution: College of Bioengineering, ChongQing University, ChongQing, 400044, P. R. China; Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw, Poland; Dipartimento di Chimica "G. Ciamician" dell'Universita, Via Selmi 2, I-40126 Bologna, Italy

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