Polarizabilities and Hyperpolarizabilities of Hydrogen Chains: Is Self-Interaction Correction the Key?

ORAL

Abstract

Semi-local density functionals like the local spin density and generalized gradient approximations are known to overestimate [1, 2] the polarizabilities and especially the hyperpolarizabilities of long-chain molecules, while these quantities are much better predicted by exact-exchange methods (Hartree-Fock or Optimized Effective Potential). The source of this failure of the semilocal approaches for the electric response is rooted in the self-interaction error inherent to the semilocal approximations. We show here that the semi-local functionals, after full or scaled-down Perdew-Zunger self-interaction correction [3, 4], are even better than the exact-exchange methods for these quantities. \newline [1] S. K\"{u}mmel, L. Kronik, J. P. Perdew, Phys. Rev. Lett. \textbf{93,} 213002 (2004). \newline [2] C. D. Pemmaraju, S. Sanvito, K. Burke, arXiv:0708.2814v1. \newline [3] J. P. Perdew, A. Zunger, Phys. Rev. B. \textbf{23}, 5048 (1981). \newline [4] O. A. Vydrov, G. E. Scuseria, A. Ruzsinszky, J. P. Perdew, G. I. Csonka, J. Chem. Phys. \textbf{124}, 094108 (2006).

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Authors

  • A. Ruzsinszky

    • Dept. of Physics, Tulane U., New Orleans LA 70118
    • Dept. of Physics,Tulane U.

  • John P. Perdew

    • Dept. of Physics, Tulane U., New Orleans LA 70118
    • Dept. of Physics,Tulane U.
    • Department of Physics and Quantum Theory Group, Tulane University
    • Department. of Physics and Quantum Theory Group, Tulane University, New Orleans, LA 70118

  • G.I. Csonka

    • Dept. of Chemistry, Budapest U. of Technology and Economics

  • G.E. Scuseria

    • Dept. of Chemistry, Rice U.

  • O.A. Vydrov

    • Dept. of Chemistry, MIT