Size-dependent polarizabilities and van der Waals dispersion coefficients of fullerenes from large-scale complex...

While the anomalous non-additive size-dependencies of static dipole polarizabilities and van der Waals C₆ dispersion coefficients of carbon fullerenes are well established, the widespread reported scalings for the latter (ranging from N^2.2 to N^2.8) call for a comprehensive first-principles investigation. With a highly efficient implementation of the linear complex polarization propagator, we have performed Hartree-Fock and Kohn-Sham density functional theory calculations of the frequency-dependent polarizabilities for fullerenes consisting of up to 540 carbon atoms. Our results for the static polarizabilities and C₆ coefficients show scalings of N^1.2 and N^2.2, respectively, thereby deviating significantly from the previously reported values obtained with the use of semi-classical/empirical methods. Arguably, our reported values are the most accurate to date as they represent the first ab initio or first-principles treatment of fullerenes up to a convincing system size.