Infrared study of diluted solutions of polyatomic molecules. I. Band shape of fundamentals associated with nondegenerate normal modes

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Abstract
A theory is proposed to analyze the band shapes of the simplest class of ir band profiles of polyatomic molecule solutions. The following theoretical points are explored in detail: dependence of vibrational correlation functions on the nature of normal modes involved, calculation of vectorial correlation functions for a classical ensemble of free asymmetric rotators, construction of extended diffusion models for asymmetric tops, and use of the ordered cumulant expansion techniques to study anisotropic rotational diffusion in liquids. The theory predicts a large variety of complex, often highly irregular, band profiles. A catalogue of representative band profiles is presented which orders them according to the symmetry of the active molecule.