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• W2024007252 abstract "To develop a correlation-free reduced form of torsion-rotation Hamiltonian that is suitable for analyzing observed spectra for methanol and its isotopic species, the origin of various classes of correlation problems often encountered in fitting the molecular constants to experimental data are analyzed for a molecule with an internal rotation. It is shown that the correlation problems can be completely eliminated by considering either the data set or the reduction of the Hamiltonian together with practical considerations, where an appropriate definition of order of magnitude plays an important role. For a molecule with C3v(M) symmetry such as methanol and its isotopic species, it is found that some terms which are included in the traditional or a reduced Hamiltonian given so far should not be used simultaneously. For example, the traditional terms k5Pa2(1−cos 3γ) and k6Pa{Pγ,1−cos 3γ} should not be used simultaneously as adjustable ones and one of three traditional terms k6Pa{Pγ,1−cos 3γ}, k7{Pγ2,1−cos 3γ}, and (V6/2)(1−cos 6γ) must be constrained. A proposed correlation-free Hamiltonian is tested for its usefulness by analyzing observed data for O-18 methanol. Total 424 microwave lines with vt⩽2, J⩽20, and K⩽9 are globally fitted to an root-mean square (RMS) deviation of 0.234 MHz including the Q-branch transitions for A species with vt=1 and K=9←8 which are successfully fitted to the experimental accuracy." @default.
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• W2024007252 date "1999-01-08" @default.
• W2024007252 modified "2023-09-22" @default.
• W2024007252 title "Correlation problems and a correlation-free torsion-rotation Hamiltonian for a molecule with an internal rotor" @default.
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• W2024007252 doi "https://doi.org/10.1063/1.478060" @default.
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