Orbital-dependent correlation energy in density-functional theory based on a second-order perturbation approach: Success and failure
10.1063/1.1904584
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

We have developed a second-order perturbation theory (PT) energy functional within density-functional theory (DFT). Based on PT with the Kohn–Sham (KS) determinant as a reference, this new ab initio exchange-correlation functional includes an exact exchange (EXX) energy in the first order and a correlation energy including all single and double excitations from the KS reference in the second order. The explicit dependence of the exchange and correlation energy on the KS orbitals in the functional fits well into our direct minimization approach for the optimized effective potential, which is a very efficient method to perform fully self-consistent calculations for any orbital-dependent functionals. To investigate the quality of the correlation functional, we have applied the method to selected atoms and molecules. For two-electron atoms and small molecules described with small basis sets, this new method provides excellent results, improving both second-order Møller–Plesset expression and any conventional DFT results significantly. For larger systems, however, it performs poorly, converging to very low unphysical total energies. The failure of PT based energy functionals is analyzed, and its origin is traced back to near degeneracy problems due to the orbital- and eigenvalue-dependent algebraic structure of the correlation functional. The failure emerges in the self-consistent approach but not in perturbative post-EXX calculations, emphasizing the crucial importance of self-consistency in testing new orbital-dependent energy functionals.

Bibliography

Mori-Sánchez, P., Wu, Q., & Yang, W. (2005). Orbital-dependent correlation energy in density-functional theory based on a second-order perturbation approach: Success and failure. The Journal of Chemical Physics, 123(6).

Authors 3
  1. Paula Mori-Sánchez (first)
  2. Qin Wu (additional)
  3. Weitao Yang (additional)
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Dates
Type When
Created 20 years ago (Aug. 15, 2005, 6:05 p.m.)
Deposited 2 years ago (Aug. 1, 2023, 9:45 p.m.)
Indexed 3 weeks, 1 day ago (Aug. 6, 2025, 8:46 a.m.)
Issued 20 years ago (Aug. 8, 2005)
Published 20 years ago (Aug. 8, 2005)
Published Online 20 years ago (Aug. 17, 2005)
Published Print 20 years ago (Aug. 8, 2005)
Funders 0

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@article{Mori_S_nchez_2005, title={Orbital-dependent correlation energy in density-functional theory based on a second-order perturbation approach: Success and failure}, volume={123}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1904584}, DOI={10.1063/1.1904584}, number={6}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Mori-Sánchez, Paula and Wu, Qin and Yang, Weitao}, year={2005}, month=aug }