On the Theoretical Quantification of Radii of Atoms in Molecules

Despite the fundamental importance of radii of atoms in molecules for numerous applications in physics and chemistry, comprehensive methods for their theoretical evaluation are still scarce. Here, we present quantum chemistry-based approaches for evaluation of radii of atoms in molecules and assess their robustness by studying the agreement of van der Waals and solvent-excluded surfaces constructed by them with reference molecular surfaces. By studying a large dataset of 1235 molecules, we show that estimation of radii via effective and free atomic volumes can accurately take the dependence of atomic radii on the chemical environment into account.