Effective torsion-rotation Hamiltonian for methanol-type molecules

A fourth-order effective Hamiltonian has been derived for the torsion-rotation problem of a methanol-type molecule, i.e., for a C_3v top attached to a C_s frame. First, symmetry considerations based on a frame-fixed axis system are used to determine allowed terms in the Hamiltonian. These terms are then subjected to a contact transformation to remove the indeterminate ones. This procedure is essentially an extension of Watson's method for semirigid molecules to the torsion-rotation problem. It is demonstrated that the Hamiltonian derived in the present work is capable of improving the fittings of the millimeter and submillimeter absorption frequencies of CH₃OH and CH₃SH.