Feature of Exact Exchange Kohn-Sham Orbitals with Krieger-Li-Iafrate Approximation

Cited 13 time in webofscience Cited 12 time in scopus
  • Hit : 383
  • Download : 407
We report feature of Kohn-Sham (KS) molecular orbitals computed with the Krieger-Li-Iafrate (KLI) approximation for exact exchange through the comparison to the results of Hartree-Fock (HF) and other KS methods such as local density approximation (LDA) and generalized gradient approximation (GGA). KLI occupied orbitals have similar energies and shapes with those of HF. KLI virtual orbitals are likely to form bound states with negative eigenvalues due to the correct -1/r asymptotic behavior of KLI potentials, whereas HF virtual orbitals are mostly unbound. As a result, HF orbitals tend to be diffuse because of their plane-wave-like nature, and their energies are highly sensitive to the size of basis set. The energies of LDA/GGA orbitals appear to be upshifted by a constant factor from the KLI results, but they also produce unbound virtual orbitals like HF. The energy gaps between KLI occupied and virtual orbitals are very close to the corresponding experimental excitation energies compared to the other methods. We also show that Brillouin's theorem can be applied to a Slater determinant made of KLI orbitals as a corollary of the KLI approximation.
Publisher
WILEY-V C H VERLAG GMBH
Issue Date
2015-03
Language
English
Article Type
Article
Keywords

DENSITY-FUNCTIONAL THEORY; MULTIREFERENCE CONFIGURATION-INTERACTION; MULTIDETERMINANTAL WAVE-FUNCTIONS; MOLECULAR-EXCITATION ENERGIES; SELF-INTERACTION CORRECTION; EFFECTIVE-POTENTIAL METHOD; SINGLE-ELECTRON BASIS; CAS-DFT; STATES; COMBINATION

Citation

BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.36, no.3, pp.998 - 1007

ISSN
0253-2964
DOI
10.1002/bkcs.10189
URI
http://hdl.handle.net/10203/198702
Appears in Collection
CH-Journal Papers(저널논문)
Files in This Item
ART001971039.pdf(936.59 kB)Download
This item is cited by other documents in WoS
⊙ Detail Information in WoSⓡ Click to see webofscience_button
⊙ Cited 13 items in WoS Click to see citing articles in records_button

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0