Effects of perturbation order and basis set on alchemical predictions

TL;DR

This paper examines how the choice of basis set and perturbation order affects the accuracy of alchemical predictions in density functional theory, proposing corrections and analyzing results on diatomic molecules.

Contribution

It introduces an error estimation method based on electron density, proposes a basis-set correction, and evaluates alchemical predictions up to fifth order on diatomic molecules.

Findings

Near CCSD accuracy in predicting binding energies and vibrational frequencies

Basis-set incompleteness significantly impacts prediction accuracy

Perturbation order up to fifth provides reliable results

Abstract

Alchemical perturbation density functional theory has been shown to be an efficient and computationally inexpensive way to explore chemical compound space. We investigate approximations made, in terms of atomic basis sets and perturbation order,introduce an electron-density based estimate of errors of the alchemical prediction, and propose a correction for effects due to basis-set incompleteness. Our numerical analysis of potential energy estimates, and resulting binding curves, is based on CCSD reference results, and is limited to all neutral diatomics with 14 electrons (AlH ... N$_2$). The method predicts binding energy, equilibrium distance, and vibrational frequencies of neighbouring out-of-sample diatomics with near CCSD quality using perturbations up to 5$^{th}$ order. We also discuss simultaneous alchemical mutations at multiple sites in benzene.