Fractional charge behavior and band gap predictions with the XYG3 type of doubly hybrid density functionals.

Journal Article (Journal Article)

In this work, we examine the fractional charge behaviors of doubly hybrid (DH) functionals. By plotting the ground-state energies E and energy derivatives for atoms and molecules with fractional electron numbers N, we directly quantify the delocalization errors of some representative DH functionals such as B2PLYP, XYG3, and XYGJ-OS. Numerical assessments on ionization potentials (IPs), electron affinities (EAs), and fundamental gaps, from either integer number calculations or energy derivative calculations, are provided. It is shown that the XYG3 type of DH functionals gives good agreement between their energy derivatives and the experimental IPs, EAs, and gaps, as expected from their nearly straight line fractional charge behaviors.

Full Text

Duke Authors

Cited Authors

  • Su, NQ; Yang, W; Mori-Sánchez, P; Xu, X

Published Date

  • October 2014

Published In

Volume / Issue

  • 118 / 39

Start / End Page

  • 9201 - 9211

PubMed ID

  • 24844969

Electronic International Standard Serial Number (EISSN)

  • 1520-5215

International Standard Serial Number (ISSN)

  • 1089-5639

Digital Object Identifier (DOI)

  • 10.1021/jp5029992


  • eng