On the Physical Interpretation of Torsion-Rotation Parameters in Methanol and Acetaldehyde: Comparison of Global Fit and Ab Initio Results

Published

February 22, 1999

Author(s)

L H. Xu, R M. Lees, Jon T. Hougen

Abstract

Equilibrium structural constants and certain torsion-rotation interaction parameters have been determined for methanol and acetaldehyde from ab initio calculations using Gaussian 94. The substantial molecular flexing which occurs in going from the bottom to the top of the torsional potential barrier can be quantitatively related to coefficients of torsion-rotation terms having a (1 - cos3g) dependence on torsional angle g. The barrier height, six equilibrium structural constants characterizing the bottom of the potential well, and six torsion-rotation constants are all compared to experimental parameters obtained from global fits to large microwave and far-infrared data sets for methanol and acetaldehyde. The rather encouraging agreement between the Gaussian and global fit results serves both to validate the accuracy of ab initio calculations of these parameters, and to demonstrate that the physical origin of the torsion-rotation interaction terms lies primarily in structural relaxation with torsion.

Citation

Journal of Chemical Physics

Pub Type

Journals

Keywords

ab initio, acetaldehyde, global fit, internal rotation barrier, methanol, torsion-rotation parameters

Citation

Xu, L. , Lees, R. and Hougen, J. (1999), On the Physical Interpretation of Torsion-Rotation Parameters in Methanol and Acetaldehyde: Comparison of Global Fit and Ab Initio Results, Journal of Chemical Physics (Accessed December 3, 2024)