From ab initio data to high-dimensional potential energy surfaces: A critical overview and assessment of the development of permutationally invariant polynomial potential energy surfaces for single molecules.

The representation of high-dimensional potential energy surfaces by way of the many-body expansion and permutationally invariant polynomials has become a well-established tool for improving the resolution and extending the scope of molecular simulations. The high level of accuracy that can be attained by these potential energy functions (PEFs) is due in large part to their specificity: for each term in the many-body expansion, a species-specific training set must be generated at the desired level of theory and a number of fits attempted in order to obtain a robust and reliable PEF. In this work, we attempt to characterize the numerical aspects of the fitting problem, addressing questions which are of simultaneous practical and fundamental importance. These include concrete illustrations of the nonconvexity of the problem, the ill-conditionedness of the linear system to be solved and possible need for regularization, the sensitivity of the solutions to the characteristics of the training set, and limitations of the approach with respect to accuracy and the types of molecules that can be treated. In addition, we introduce a general approach to the generation of training set configurations based on the familiar harmonic approximation and evaluate the possible benefits to the use of quasirandom sequences for sampling configuration space in this context. Using sulfate as a case study, the findings are largely generalizable and expected to ultimately facilitate the efficient development of PIP-based many-body PEFs for general systems via automation.