Effect of Fluorine Substitution on Magnetizabilities: Insights from Density Functional Theory and Benchmark Coupled-Cluster Calculations.

Abstract

The quantitative calculation of the magnetizability tensor of fluorine-containing molecules has been a longstanding challenge for quantum chemistry. We report a benchmark study on the effect of fluorine substitution on the magnetizability (both isotropic and anisotropic) of 24 small closed-shell molecules using coupled-cluster (CCSD(T)) theory, large basis sets, and London atomic orbitals. By extrapolation to a complete basis set (CBS) result, we establish the CCSD(T)/CBS limit and take the opportunity to assess the performance of various density functional theory approximations. Correcting for zero-point vibration further allows us to directly compare theory with (gas-phase) experimental data. We revisit Flygare's hypothesis on molecular magnetizabilities, which relates the successive replacement of hydrogen by fluorine atoms to changes in the magnetizability anisotropy. Some exceptions to this hypothesis are documented, and we rationalize these observations on the basis of hybridization on carbon.