English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation

MPS-Authors
/persons/resource/persons21311

Atalla,  Viktor
Theory, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons54404

Zhang,  Igor Ying
Theory, Fritz Haber Institute, Max Planck Society;

/persons/resource/persons21637

Hofmann,  Oliver T.
Theory, Fritz Haber Institute, Max Planck Society;
Institute of Solid State Physics, Graz University of Technology;

/persons/resource/persons21998

Ren,  Xinguo
Theory, Fritz Haber Institute, Max Planck Society;
Key Laboratory of Quantum Information, University of Science and Technology of China;

/persons/resource/persons22010

Rinke,  Patrick
Theory, Fritz Haber Institute, Max Planck Society;
COMP/Department of Applied Physics, Aalto University;

/persons/resource/persons22064

Scheffler,  Matthias
Theory, Fritz Haber Institute, Max Planck Society;

External Ressource
No external resources are shared
Fulltext (public)

PhysRevB.94.035140.pdf
(Publisher version), 2MB

Supplementary Material (public)
There is no public supplementary material available
Citation

Atalla, V., Zhang, I. Y., Hofmann, O. T., Ren, X., Rinke, P., & Scheffler, M. (2016). Enforcing the linear behavior of the total energy with hybrid functionals: Implications for charge transfer, interaction energies, and the random-phase approximation. Physical Review B, 94(3): 035140. doi:10.1103/PhysRevB.94.035140.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002B-0F9C-B
Abstract
We obtain the exchange parameter of hybrid functionals by imposing the fundamental condition of a piecewise linear total energy with respect to electron number. For the Perdew-Burke-Ernzerhof (PBE) hybrid family of exchange-correlation functionals (i.e., for an approximate generalized Kohn-Sham theory) this implies that (i) the highest occupied molecular orbital corresponds to the ionization potential (I), (ii) the energy of the lowest unoccupied molecular orbital corresponds to the electron affinity (A), and (iii) the energies of the frontier orbitals are constant as a function of their occupation. In agreement with a previous study [N. Sai et al., Phys. Rev. Lett. 106, 226403 (2011)], we find that these conditions are met for high values of the exact exchange admixture α and illustrate their importance for the tetrathiafulvalene-tetracyanoquinodimethane complex for which standard density functional theory functionals predict artificial electron transfer. We further assess the performance for atomization energies and weak interaction energies. We find that atomization energies are significantly underestimated compared to PBE or PBE0, whereas the description of weak interaction energies improves significantly if a 1/R6 van der Waals correction scheme is employed.