Canonical force field theory in terms of curvilinear internal coordinates: Application to the methane molecule

Abstract

This Letter generalizes the Kuczera’s theory of the vibrational canonical force field in order to obtain an unambiguous and uniquely defined expression for the anharmonic force field in terms of curvilinear internal coordinates. By using this generalization it has been shown mathematically that the canonical force constants could be transferred between molecules with the same geometrical structure. As illustration, the theory is used to obtain the expressions for the quadratic and cubic canonical force constants of the methane molecule.