FITTING OF ASYMMETRIC TOP ROTATIONAL ENERGIES (PART II)

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1975

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Ohio State University

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A reduced Hamiltonian (AS) was $developed^{1}$ to fit rotational energy levels for asymmetric tops; however, this Hamiltonian could break down for near-symmetric tops. Two methods of overcoming this difficulty are to change to a reduced Hamiltonian (NS) that is valid in the symmetric top $limit^{2}$ or to change representations; these methods are discussed in more detail, with applications to the spectra of several molecules. Under certain conditions the usual technique for assignment of the quantum labels $J_{{K}_{a}{K}_{c}}$ to energy levels can be done incorrectly. Several resolutions of this problem, including one that speeds greatly the calculation of molecular constants for certain near-symmetric top molecules, are presented.

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$^{1}$ J.K.G, Watson, J. Chem. Phys. 46, 1935 (1967). $^{2}$ Twenty-ninth Symposium on Molecular Structure and Spectroscopy, The Ohio State University, June 1974, paper ME10. Present address of James K. G. Watson: Department of Chemistry, The University, Southampton SO9 5NH, England.""
Author Institution: Department of Physics, The Ohio State University

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