Effects of perturbation order and basis set on alchemical predictions

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.

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• Heuristics and Uncertainty Quantification in Rational and Inverse Compound and Catalyst Design
• Extending the definition of atomic basis sets to atoms with fractional nuclear charge
• Antisymmetry rules of response properties in certain chemical spaces