Local reduced-density-matrix-functional theory: Incorporating static correlation effects in Kohn-Sham equations

Lathiotakis, N.N.; Helbig, N.; Rubio, A.; Gidopoulos, N.I.

Abstract

We propose a scheme to bring reduced-density-matrix-functional theory into the realm of density functional theory (DFT) that preserves the accurate density functional description at equilibrium, while incorporating accurately static and left-right correlation effects in molecules and keeping the good computational performance of DFT-based schemes. The key ingredient is to relax the requirement that the local potential is the functional derivative of the energy with respect to the density. Instead, we propose to restrict the search for the approximate natural orbitals within a domain where these orbitals are eigenfunctions of a single-particle Hamiltonian with a local effective potential. In this way, fractional natural occupation numbers are accommodated into Kohn-Sham equations allowing for the description of molecular dissociation without breaking spin symmetry. Additionally, our scheme provides a natural way to connect an energy eigenvalue spectrum to the approximate natural orbitals and this spectrum is found to represent accurately the ionization potentials of atoms and small molecules.

Citation

Lathiotakis, N., Helbig, N., Rubio, A., & Gidopoulos, N. (2014). Local reduced-density-matrix-functional theory: Incorporating static correlation effects in Kohn-Sham equations. Physical Review A, 90(3), Article 032511. https://doi.org/10.1103/physreva.90.032511

• Journal Article Type: Article
• Acceptance Date: Apr 28, 2014
• Online Publication Date: Sep 24, 2014
• Publication Date: Sep 24, 2014
• Deposit Date: Sep 26, 2014
• Publicly Available Date: Oct 2, 2014
• Journal: Physical Review A - Atomic, Molecular, and Optical Physics
• Print ISSN: 1050-2947
• Electronic ISSN: 1094-1622
• Publisher: American Physical Society
• Peer Reviewed: Peer Reviewed
• Volume: 90
• Issue: 3
• Article Number: 032511
• DOI: https://doi.org/10.1103/physreva.90.032511
• Public URL: https://durham-repository.worktribe.com/output/1453568
• Related Public URLs: http://arxiv.org/abs/1407.7128