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Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2021

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

Résumé

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.
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Dates et versions

hal-03324105 , version 1 (31-01-2022)

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Jacques Desmarais, Alessandro Erba, Jean-Pierre Flament, Bernard Kirtman. Perturbation Theory Treatment of Spin–Orbit Coupling II: A Coupled Perturbed Kohn–Sham Method. Journal of Chemical Theory and Computation, 2021, 17 (8), pp.4712-4732. ⟨10.1021/acs.jctc.1c00460⟩. ⟨hal-03324105⟩
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