THE EFFECT OF CURVILINEAR VERSUS RECTILINEAR KINETIC ENERGY OPERATORS ON THE VIBRATION-ROTATION EIGENVALUES OF QUASI-LINEAR MOLECULES.

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1969

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Ohio State University

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Abstract

The kinetic energy operator is obtained for a nonlinear triatomic molecule of $C_{2v}$ symmetry with two degrees of freedom. These are rotation about the axis whose moment vanishes as the molecule becomes linear plus bending of the valence angle with no assumptions about amplitudes. Vibration-rotation eigenvalues are obtained in the case of small amplitude (nearly rectilinear) motion and in the case of large amplitude (curvilinear) motion. Comparison of the results illuminates the fallacy of placing the entire burden of anharmonicity upon the potential energy function. This point is further illustrated with a determination of the barrier to linearity in sulfur dioxide by fitting infrared data to the eigenvalues obtained in each of the cases mentioned.

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This work was supported in part by the National Science Foundation.
Author Institution: Department of Chemistry, Clemson University

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