THE STRUCTURE OF $n\upsilon_{3}$ OVERTONE LEVELS IN SPHERICAL-TOP MOLECULES
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Date
1982
Journal Title
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Publisher
Ohio State University
Abstract
Anharmonic Structures of $n\upsilon_{3}$ overtones of spherical tops lie between two extreme categories. In the ""polar"" limit the major second-order perturbation is the vibrational annular momentum, ${\stackrel{\ell}{\sim}^{2}}_{3}$, so the dominant splitting is proportional to $\ell_{3}(\ell_{3}+1)$. ${SIF_{4}}^{1}$ seems to exhibit this behavior. In the ""Carteslan"" or ""local-mode"" limit a different anharmonic term dominates, producing extraordinary patterns of degeneracies and splitting ratios. Force-field models for hexafluorldes $^{A}XF_{6}$ with a central atom whose mass is at least as great as that of Mo $(A \geq 100)$ appear to fall near this extreme. $^{32}SF_{6}$ is an intermediate case. Properties of the vibrational levels in the limits will be discussed, and illustrations of $n\upsilon_{3}$ ladders will be compared.
Description
$^{1}$A.S. Plne, private communication, 1981.