ao7b00802_si_002.xlsx (54.57 kB)

# Relativistic Effects in the Electronic Structure of Atoms

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posted on 2017-09-22, 08:13 authored by Hiroshi Tatewaki, Shigeyoshi Yamamoto, Yasuyo HatanoPeriodic trends in
relativistic effects are investigated from

_{1}H through_{103}Lr using Dirac–Hartree–Fock and nonrelativistic Hartree–Fock calculations. Except for_{46}Pd (4d^{10}) (5s^{0}), all atoms have as outermost shell the ns or n’p spinors/orbitals. We have compared the relativistic spinor energies with the corresponding nonrelativistic orbital energies. Apart from_{24}Cr (3d^{5}) (4s^{1}),_{41}Nb (4d^{4}) (5s^{1}), and_{42}Mo (4d^{5}) (5s^{1}), the ns_{+}spinor energies are lower than the corresponding ns orbital energies for all atoms having ns spinor (ns_{+}) as the outermost shell, as some preceding works suggested. This indicates that kinematical effects are larger than indirect relativistic effects (the shielding effects of the ionic core plus those due to electron–electron interactions among the valence electrons). For all atoms having np_{+}spinors as their outermost shell, in contrast, the np_{+}spinor energies are higher than the corresponding np orbital energies as again the preceding workers suggested. This implies that indirect relativistic effects are greater than kinematical effects. In the neutral light atoms, the np_{–}spinor energies are close to the np_{+}spinor energies, but for the neutral heavy atoms, the np_{–}spinor energies are considerably lower than the np_{+}spinor energies (similarly, the np_{–}spinors are considerably tighter than the np_{+}spinors), indicating the importance of the direct relativistic effects in np_{–}. In the valence nd and nf shells, the spinor energies are always higher than the corresponding orbital energies, except for_{46}Pd (4d^{10}) (5s^{0}). Correspondingly, the nd and nf spinors are more diffuse than the nd and nf orbitals, except for_{46}Pd.