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Relativistic two-electron atomic and molecular energies using LS coupling and double groups: Role of the triplet
Péter Jeszenszki1, Edit Mátyus1
1ELTE, Eötvös Loránd University, Institute of Chemistry, Pázmány Péter sétány 1/A, Budapest H-1117, Hungary.
Abstract:
The triplet contribution is computed to the 1 and 2 S0e1 states of the He atom, to the 1S0e1 state of the Li+ and Be2+ ions, and to the X1Σg + ground state of the H2 molecule by extensive use of double-group symmetry (equivalent to LS coupling for the atomic systems) during the course of the variational solution of the no-pair Dirac-Coulomb-Breit (DCB) wave equation. The no-pair DCB energies are converged within sub-parts-per-billion relative precision, using an explicitly correlated Gaussian basis optimized to the non-relativistic energies. The α fine-structure constant dependence of the triplet sector contribution to the variational energy is α4Eh at leading order, in agreement with the formal perturbation theory result available from the literature.
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