SciPost Chemistry

SciPost Chem. 1, 004 (2022) · published 10 June 2022

• doi: 10.21468/SciPostChem.1.2.004
• pdf
• BiBTeX
• RIS
• Submissions/Reports
• 

Abstract

As a new approach to efficiently describe correlation effects in the relativistic quantum world we propose to consider reduced density matrix functional theory, where the key quantity is the first-order reduced density matrix (1-RDM). In this work, we first introduce the theoretical foundations to extend the applicability of this theory to the relativistic domain. Then, using the so-called no-pair (np) approximation, we arrive at an approximate treatment of the relativistic effects by focusing on electronic wavefunctions and neglecting explicit contributions from positrons. Within the np approximation the theory becomes similar to the nonrelativistic case, with as unknown only the functional that describes the electron-electron interactions in terms of the 1-RDM. This requires the construction of functional approximations, and we therefore also present the relativistic versions of some common RDMFT approximations that are used in the nonrelativistic context and discuss their properties.

• Benavides-Riveros, Orbital-free quasidensity functional theory
  Phys. Rev. Research 6, 013060 (2024) [Crossref]
• Lew-Yee et al., Electron Correlation in the Iron(II) Porphyrin by Natural Orbital Functional Approximations
  J. Chem. Theory Comput. 19, 211 (2023) [Crossref]
• Denawi et al., GW density matrix for estimation of self-consistent GW total energies in solids
  Phys. Rev. B 108, 125107 (2023) [Crossref]
• Rivero Santamaría et al., Time evolution of natural orbitals in ab initio molecular dynamics
  160, 071102 (2024) [Crossref]
• Rodríguez-Mayorga et al., Relativistic effects on electronic pair densities: A perspective from the radial intracule and extracule probability densities
  157, 194301 (2022) [Crossref]
• Huan Lew-Yee et al., Outstanding improvement in removing the delocalization error by global natural orbital functional
  158, 084110 (2023) [Crossref]
• Mercero et al.,
  88, 229 (2023) [Crossref]
• Liebert et al., Refining and relating fundamentals of functional theory
  158, 214108 (2023) [Crossref]
• Benavides-Riveros et al., Extracting many-body quantum resources within one-body reduced density matrix functional theory
  Phys. Rev. Research 6, L012052 (2024) [Crossref]