The concept of canonical molecular force field

The purpose of this paper is to show the concept of vibrational canonical force field from an intuitive and heuristic point of view. The physical meaning and the mathematical properties of this force field are illustrated by means of the most-simple case of redundant coordinates, i.e. a system having one vibrational degree of freedom whose vibrational motion is described by means of two redundant coordinates. The results obtained in this example are generalized to the case of a system with several degrees of freedom by means of the matrix formulation. This generalization allows to obtain results that are valid for any number of degrees of freedom. q 2004 Elsevier B.V. All rights reserved.