Fitting Potential Energy Surfaces by Learning the Charge Density Matrix with Permutationally Invariant Polynomials.

Abstract

The electronic energy in the Hartree-Fock (HF) theory is the trace of the product of the charge density matrix (CDM) with the one-electron and two-electron matrices represented in an atomic orbital basis, where the two-electron matrix is also a function of the same CDM. In this work, we examine a formalism of analytic representation of a generic molecular potential energy surface (PES) as a sum of a linearly parameterized HF and a correction term, the latter formally representing the electron correlation energy, also linearly parameterized, by expressing the elements of CDM using permutationally invariant polynomials (PIPs). We show on a variety of numerical examples, ranging from exemplary two-electron systems HeH+ and H3+ to the more challenging cases of methanium (CH5+) fragmentation and high-energy tautomerization of formamide to formimidic acid that such a formulation requires significantly fewer, 10-20% of PIPs, to accomplish the same accuracy of the fit as the conventional representation at practically the same computational cost.