Antisymmetry rules of response properties in certain chemical spaces

Abstract

Understanding chemical compound space (CCS), a set of molecules and materials, is crucial for the rational discovery of molecules and materials. Concepts of symmetry have recently been introduced into CCS to account for near degeneracies and differences in electronic energies between iso-electronic materials. In this work, we present approximate relationships of response properties based on a first-principles view of CCS. They have been derived from perturbation theory and antisymmetry considerations involving nuclear charges. These rules allow approximate predictions of relative response properties of pairs of distinct compounds with opposite nuclear charge variations from a highly symmetric reference material, without the need for experiments or quantum chemical calculations of each compound. We numerically and statistically verified these rules for electric and magnetic response properties (electric dipole moment, polarizabilities, hyperpolarizabilities, and magnetizabilities) among charge-neutral and iso-electronic boron nitride-doped polycyclic aromatic hydrocarbon derivatives of naphthalene, anthracene, and pyrene. Our analysis indicates that, despite their simplicity, antisymmetry rule-based predictions are remarkably accurate, enabling dimensionality reduction of CCS. The rules predict the electric response properties more accurately than the magnetizabilities. The electric response properties in alchemical perturbation density functional theory were investigated to clarify the origin of this predictive power.