The extended Koopmans' theorem for orbital-optimized methods: Accurate computation of ionization potentials

Bozkaya U.

JOURNAL OF CHEMICAL PHYSICS, vol.139, no.15, 2013 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 139 Issue: 15
  • Publication Date: 2013
  • Doi Number: 10.1063/1.4825041
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Hacettepe University Affiliated: No


The extended Koopmans' theorem (EKT) provides a straightforward way to compute ionization potentials (IPs) from any level of theory, in principle. However, for non-variational methods, such as Moller-Plesset perturbation and coupled-cluster theories, the EKT computations can only be performed as by-products of analytic gradients as the relaxed generalized Fock matrix (GFM) and one- and two-particle density matrices (OPDM and TPDM, respectively) are required [J. Cioslowski, P. Piskorz, and G. Liu, J. Chem. Phys. 107, 6804 (1997)]. However, for the orbital-optimized methods both the GFM and OPDM are readily available and symmetric, as opposed to the standard post Hartree-Fock (HF) methods. Further, the orbital optimized methods solve the N-representability problem, which may arise when the relaxed particle density matrices are employed for the standard methods, by disregarding the orbital Z-vector contributions for the OPDM. Moreover, for challenging chemical systems, where spin or spatial symmetry-breaking problems are observed, the abnormal orbital response contributions arising from the numerical instabilities in the HF molecular orbital Hessian can be avoided by the orbital-optimization. Hence, it appears that the orbital-optimized methods are the most natural choice for the study of the EKT. In this research, the EKT for the orbital-optimized methods, such as orbital-optimized second-and third-order Moller-Plesset perturbation [U. Bozkaya, J. Chem. Phys. 135, 224103 (2011)] and coupled-electron pair theories [OCEPA(0)] [U. Bozkaya and C. D. Sherrill, J. Chem. Phys. 139, 054104 (2013)], are presented. The presented methods are applied to IPs of the second-and third-row atoms, and closed-and open-shell molecules. Performances of the orbital-optimized methods are compared with those of the counterpart standard methods. Especially, results of the OCEPA(0) method (with the aug-cc-pVTZ basis set) for the lowest IPs of the considered atoms and closed-shell molecules are substantially accurate, the corresponding mean absolute errors are 0.11 and 0.15 eV, respectively. (C) 2013 AIP Publishing LLC.