Abstract
Semilocal density functionals such as the local-spin-density and generalized-gradient approximations are known to overestimate the polarizabilities and especially the hyperpolarizabilities of long-chain molecules, the latter by as much as a factor of 10 or more in model hydrogen chains. These quantities are much better predicted by exact-exchange methods such as Hartree-Fock or optimized effective potential. We show here that the semilocal functionals, after full or scaled-down Perdew-Zunger self-interaction correction (SIC), are about as good as the exact-exchange methods for these quantities. As is the case for the exact-exchange methods, SIC is fully nonlocal and exact for all one-electron densities, and (more relevantly to the electrical response) tends to maintain an integer number of electrons on each chain unit to a greater extent than the semilocal functionals do. In this study, the SIC energy is minimized directly, without an optimized effective potential.
- Received 3 December 2007
DOI:https://doi.org/10.1103/PhysRevA.77.060502
©2008 American Physical Society