Abstract
Delocalization error has been singled out by Yang and co-workers as the dominant error in Kohn-Sham density functional theory (KS-DFT) with conventional approximate functionals. In this Letter, by computing the vertical first ionization energy for well separated He clusters, we show that multiconfiguration pair-density functional theory (MC-PDFT) is free from delocalization error. To put MC-PDFT in perspective, we also compare it with some Kohn-Sham density functionals, including both traditional and modern functionals. Whereas large delocalization errors are almost universal in KS-DFT (the only exception being the very recent corrected functionals of Yang and co-workers), delocalization error is removed by MC-PDFT, which bodes well for its future as a step forward from KS-DFT.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 5616-5620 |
| Number of pages | 5 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 8 |
| Issue number | 22 |
| DOIs | |
| State | Published - Nov 16 2017 |
Bibliographical note
Funding Information:This work was supported in part by the NSF Grant CHE-1464536. J.L.B. acknowledges a Doctor Dissertation Fellowship (DDF) provided by University of Minnesota.
Publisher Copyright:
© 2017 American Chemical Society.