English

Self-consistent range-separated density-functional theory with second-order perturbative correction via the optimized-effective-potential method

Chemical Physics 2019-12-24 v1 Computational Physics

Abstract

We extend the range-separated double-hybrid RSH+MP2 method [J. G. Angyan et al., Phys. Rev. A 72, 012510 (2005)], combining long-range HF exchange and MP2 correlation with a short-range density functional, to a fully self-consistent version using the optimized-effective-potential technique in which the orbitals are obtained from a local potential including the long-range HF and MP2 contributions. We test this approach, that we name RS-OEP2, on a set of small closed-shell atoms and molecules. For the commonly used value of the range-separation parameter μ=0.5\mu=0.5 bohr1^{-1}, we find that self-consistency does not seem to bring any improvement for total energies, ionization potentials, and electronic affinities. However, contrary to the non-self-consistent RSH+MP2 method, the present RS-OEP2 method gives a LUMO energy which physically corresponds to a neutral excitation energy and gives local exchange-correlation potentials which are reasonably good approximations to the corresponding Kohn-Sham quantities. At a finer scale, we find that RS-OEP2 gives largely inaccurate correlation potentials and correlated densities, which points to the need of further improvement of this type of range-separated double hybrids.

Keywords

Cite

@article{arxiv.1912.10893,
  title  = {Self-consistent range-separated density-functional theory with second-order perturbative correction via the optimized-effective-potential method},
  author = {Szymon Smiga and Ireneusz Grabowski and Mateusz Witkowski and Bastien Mussard and Julien Toulouse},
  journal= {arXiv preprint arXiv:1912.10893},
  year   = {2019}
}

Comments

Journal of Chemical Theory and Computation, American Chemical Society, In press

R2 v1 2026-06-23T12:54:43.386Z