Unambiguous formalism of molecular vibrations: Use of redundant coordinates and canonical matrices

This paper introduces a new approach to the problem of describing molecular vibrations in redundant valence coordinates. A consistent definition for canonical force field, which is different of that by Kuczera and Pupyshev et al., is outlined. This new definition is also generalized to other matrices like kinetic-energy matrices and transformation matrices between different sets of vibrational coordinates. The importance of such canonical matrices follows from the fact that they are uniquely determined and allow us to consider the redundant coordinates as though they were independent.