Electrical response of molecular chains from density functional theory -: art. no. 213002

The electrical response of molecular chains is dramatically overestimated by local and semilocal density functionals. We show that Kohn-Sham density-functional theory yields accurate linear and nonlinear polarizabilities when the exact exchange energy is employed together with the corresponding exact Kohn-Sham potential v(x)(r). We further show that approximations to v(x)(r) that are very accurate for the ground-state energy can nevertheless fail badly for the response because of potential barriers that have little effect on the ground-state energy but strongly affect the electron mobility.