The generalized SIC‐OEP formalism and the generalized SIC‐Slater approximation (stationary and time‐dependent cases)

Messud, Jérémie; Dinh, Phuong Mai; Reinhard, P.‐G.; Suraud, E.

doi:10.1002/andp.201100002

Cited by 11 publications

(9 citation statements)

References 72 publications

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“…The effective potential will not be the same for all orbitals and this places SIC outside the domain of Kohn-Sham DFT. It can be treated as a true Kohn-Sham functional by means of the optimized effective potential method (OEP) 35,36 , but in many applications the functional is treated in the generalized Kohn-Sham framework, i.e., the energy is minimized with respect to variation of the orbitals, resulting in different potentials for each one of them.…”

Section: Methodsmentioning

confidence: 99%

The effect of the Perdew-Zunger self-interaction correction to density functionals on the energetics of small molecules

Klüpfel

Jónsson

2012

The Journal of Chemical Physics

105

126

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Self-consistent calculations using the Perdew-Zunger self-interaction correction (PZ-SIC) to local density and gradient dependent energy functionals are presented for the binding energy and equilibrium geometry of small molecules as well as energy barriers of reactions. The effect of the correction is to reduce binding energy and bond lengths and increase activation energy barriers when bond breaking is involved. The accuracy of the corrected functionals varies strongly, the correction to the binding energy being too weak for the local density approximation but too strong for the gradient dependent functionals considered. For the Perdew, Burke, and Ernzerhof (PBE) functional, a scaling of the PZ-SIC by one half gives improved results on average for both binding energy and bond lengths. The PZ-SIC does not necessarily give more accurate total energy, but it can result in a better cancellation of errors. An essential aspect of these calculations is the use of complex orbitals. A restriction to real orbitals leads to less accurate results as was recently shown for atoms [S. Klüpfel, P. Klüpfel, and H. Jónsson, Phys. Rev. A 84, 050501 (2011)]. The molecular geometry of radicals can be strongly affected by PZ-SIC. An incorrect, non-linear structure of the C(2)H radical predicted by PBE is corrected by PZ-SIC. The CH(3) radical is correctly predicted to be planar when complex orbitals are used, while it is non-planar when the PZ-SIC calculation is restricted to real orbitals.

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Section: Methodsmentioning

confidence: 99%

The effect of the Perdew-Zunger self-interaction correction to density functionals on the energetics of small molecules

Klüpfel

Jónsson

2012

The Journal of Chemical Physics

105

126

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“…Note that the algorithm described here can also be used to optimize the Foster-Boys [57,58] spatial localization criterion in the form [60,85] …”

Section: Appendix B: Unitarily Constrained Algorithm For the Energy-mmentioning

confidence: 99%

Using complex degrees of freedom in the Kohn-Sham self-interaction correction

Hofmann

Klüpfel

et al. 2012

Phys. Rev. A

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The Perdew-Zunger self-interaction correction (SIC) to local and semilocal density functionals systematically underestimates molecular bond lengths, yet improves many other ground-state properties. An alternative definition of a SIC is reached by using the Perdew-Zunger energy with a global, multiplicative Kohn-Sham potential instead of the orbital-specific potentials of traditional SIC. Due to the unitary variance of the SIC energy, the most general construction of the SIC Kohn-Sham potential involves a unitary transformation of the Kohn-Sham orbitals. We systematically investigate the Kohn-Sham version of the SIC, in particular with respect to the bond-length question, and present a detailed analysis of the influence of different unitary transformations. Using a complex-valued energy-minimizing transformation appears to be the most favorable approach, and we explain this result by analyzing orbital densities. We discuss how to calculate the transformations efficiently.

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“…A smaller Gaussian density smearing can be used in the PPD model as a consequence of the polarizability reduction, which increases the dielectric constant and therefore largely negates the previous changes. This makes clear the need for future research on efficient self-interaction correction methods 48,51,52 for tightbinding in conjunction with the electrostatic multipoles model. We refer to the recently developed long-range corrected DFTB method 48 as a possible solution.…”

Section: Error Analysismentioning

confidence: 99%

Gaussian polarizable-ion tight binding

Boleininger

Guilbert

Horsfield

2016

The Journal of Chemical Physics

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Implementation and benchmark of a long-range corrected functional in the density functional based tightbinding method The Journal of Chemical Physics 143, 184107 (2015) To interpret ultrafast dynamics experiments on large molecules, computer simulation is required due to the complex response to the laser field. We present a method capable of efficiently computing the static electronic response of large systems to external electric fields. This is achieved by extending the density-functional tight binding method to include larger basis sets and by multipole expansion of the charge density into electrostatically interacting Gaussian distributions. Polarizabilities for a range of hydrocarbon molecules are computed for a multipole expansion up to quadrupole order, giving excellent agreement with experimental values, with average errors similar to those from density functional theory, but at a small fraction of the cost. We apply the model in conjunction with the polarizable-point-dipoles model to estimate the internal fields in amorphous poly(3-hexylthiophene-2,5-diyl). C 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license

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The generalized SIC‐OEP formalism and the generalized SIC‐Slater approximation (stationary and time‐dependent cases)

Cited by 11 publications

References 72 publications

The effect of the Perdew-Zunger self-interaction correction to density functionals on the energetics of small molecules

The effect of the Perdew-Zunger self-interaction correction to density functionals on the energetics of small molecules

Using complex degrees of freedom in the Kohn-Sham self-interaction correction

Gaussian polarizable-ion tight binding

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