Title :

Perturbation Theory Treatment of Spin–Orbit Coupling II: A Coupled Perturbed Kohn–Sham Method

Author(s) :

Desmarais, Jacques [Auteur correspondant]
Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux [IPREM]
Università degli studi di Torino = University of Turin [UNITO]
Erba, Alessandro [Auteur]
Università degli studi di Torino = University of Turin [UNITO]
Flament, Jean-Pierre [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Kirtman, Bernard [Auteur correspondant]
Department of Chemistry and Biochemistry [Santa Barbara]

Journal title :

Journal of Chemical Theory and Computation

Pages :

4712-4732

Publisher :

American Chemical Society

Publication date :

2021-08-10

ISSN :

1549-9618

HAL domain(s) :

Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

English abstract : [en]

A noncanonical coupled perturbed Kohn–Sham density functional theory (KS-DFT)/Hartree-Fock (HF) treatment of spin–orbit coupling (SOC) is provided. We take the scalar-relativistic KS-DFT/HF solution, obtained with a ...
Show more >A noncanonical coupled perturbed Kohn–Sham density functional theory (KS-DFT)/Hartree-Fock (HF) treatment of spin–orbit coupling (SOC) is provided. We take the scalar-relativistic KS-DFT/HF solution, obtained with a relativistic effective core potential, as the zeroth-order approximation. Explicit expressions are given for the total energy through the 4th order, which satisfy the 2n + 1 rule. Second-order expressions are provided for orbital energies and density variables of spin-current DFT. Test calculations are carried out on the halogen homonuclear diatomic and hydride molecules, including 6p and 7p elements, as well as open-shell negative ions. The computed properties through second or third order match well with those from reference two-component self-consistent field calculations for total and orbital energies as well as spin-current densities. In only one case (At2–) did a significant deviation occur for the remaining density variables. Our coupled perturbation theory approach provides an efficient way of adding the effect of SOC to a scalar-relativistic single-reference KS-DFT/HF treatment, in particular because it does not require diagonalization in the two-component spinor basis, leading to saving factors on the number of required floating-point operations that may exceed one order of magnitude.Show less >

Language :

Anglais

Popular science :

Non

Collections :

• Laboratoire de Physique des Lasers, Atomes et Molécules (PhLAM) - UMR 8523

Source :

Harvested from HAL