The Journal of Chemical Physics · 1963 · 142 citations · 7 references
Natural SciencesChemistryPhysicsPhysical ChemistryQuantum ChemistryQuantum MechanicsElectron ConfigurationsElectron CorrelationElectronic StructureHartree-fock TheoryOpen-shell SystemsStrongly Correlated Electron SystemsCorrelationElectron Correlation EffectsElectron Correlation EnergyElectron Correlation In Open-shell SystemsElectronic CorrelationsGround-state CorrelationHartree-fock EnergyStrongly Correlated Electrons
The study estimates the ground‑state correlation energy for the second‑row isoelectronic series of atoms. The authors use recently calculated relativistic and Hartree–Fock energies for closed‑ and open‑shell configurations to estimate the correlation energy. The second‑row correlation energy mirrors the first‑row characteristics, with electron pairing in a given orbital providing the main contribution, intrashell correlation dominating over intershell correlation, and 3s–3s correlation varying linearly with Z.
The correlation energy for the ground-state isoelectronic series of the second-row atoms of the periodic table are estimated. In this estimate the relativistic energies for the closed and the open shells, and the Hartree—Fock energies are taken from calculations we have recently performed. As expected, the second-row correlation energy parallels, in general, the characteristics of the first-row correlation energy. The principal contribution to the correlation energy is due to pairing of electrons in a given orbital. The intershell correlation is smaller than the intrashell correlation (but not negligible) and the 3s—3s electron correlation is linear in Z.
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