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LANS Publications

"Permutationally Invariant Polynomial Basis for Molecular Energy Surface Fitting via Monomial Symmetrization"

Z. Xie and J. M. Bowman

Journal of Chemical Theory and Computation, vol. 6, no. 1, , pp. 26-34. Also Preprint ANL/MCS-P1674-0909

Preprint Version: [pdf]

We describe a procedure to develop a fitting basis for molecular potential energy surfaces (PES) that is invariant with respect to permutation of like atoms. The method is based on a straightforward symmetrization of a primitive monomial basis and is illustrated for several classes of molecules. A numerically efficient method to evaluate the resulting expression for the PES is also described. The fitting basis is used to obtain a new PES for H3O+ based on roughly 62 000 ab initio energies.