Electrical response of molecular chains from density functional theory.
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 upsilonx(r). We further show that approximations to upsilonx(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.
Kümmel
Stephan
S
Max-Planck-Institut für Physik komplexer Systeme, Nöthnitzer Strasse 38, D-01187 Dresden, Germany.
Kronik
Leeor
L
Perdew
John P
JP