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 data
set of 1235 molecules, it is shown that estimation of radii via effective
and free atomic volumes can accurately take the dependence of atomic
radii on the chemical environment into account.