Efficient generation of sum-of-products representations of high-dimensional potential energy surfaces based on multimode expansions.

The transformation of multi-dimensional potential energy surfaces (PESs) from a grid-based multimode representation to an analytical one is a standard procedure in quantum chemical programs. Within the framework of linear least squares fitting, a simple and highly efficient algorithm is presented, which relies on a direct product representation of the PES and a repeated use of Kronecker products. It shows the same scalings in computational cost and memory requirements as the potfit approach. In comparison to customary linear least squares fitting algorithms, this corresponds to a speed-up and memory saving by several orders of magnitude. Different fitting bases are tested, namely, polynomials, B-splines, and distributed Gaussians. Benchmark calculations are provided for the PESs of a set of small molecules.