Molecular potential energy surfaces by interpolation in Cartesian coordinates

We present a new method for expressing a molecular potential energy surface (PES) as an interpolation of local Taylor expansions. By using only Cartesian coordinates for the atomic positions, this method avoids redundancy problems associated with the use of internal coordinates. The correct translation, rotation, inversion, and permutation invariance are incorporated in the PES via the interpolation method itself. The method is most readily employed for bound molecules or clusters and is demonstrated by application to the vibrational motion of acetylene. (C) 1998 American Institute of Physics.